Transparent conductors incorporating additives and related manufacturing methods

ABSTRACT

A transparent conductor includes a film of a conductive ceramic and conductive additives at least partially incorporated into the film and localized within a region of the film. A thickness of the region is less than an overall thickness of the film, and at least one of the conductive additives has an aspect ratio of at least 3. The transparent conductor has a sheet resistance that is less than an intrinsic sheet resistance of the film.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.13/536,968, filed on Jun. 28, 2012, which claims the benefit of U.S.Provisional Application No. 61/502,169, filed on Jun. 28, 2011, U.S.Provisional Application No. 61/547,983, filed on Oct. 17, 2011, U.S.Provisional Application No. 61/502,174, filed on Jun. 28, 2011, U.S.Provisional Application No. 61/547,995, filed on Oct. 17, 2011, U.S.Provisional Application No. 61/502,180, filed on Jun. 28, 2011, U.S.Provisional Application No. 61/548,001, filed on Oct. 17, 2011, U.S.Provisional Application No. 61/560,475, filed on Nov. 16, 2011, and U.S.Provisional Application No. 61/563,454, filed on Nov. 23, 2011, thedisclosures of which are incorporated herein by reference in theirentireties.

FIELD OF THE INVENTION

The invention relates generally to structures incorporating additives.More particularly, the invention relates to transparent conductorsincorporating additives to impart improved functionality such aselectrical conductivity.

BACKGROUND

A transparent conductor permits the transmission of light whileproviding a conductive path for an electric current to flow through adevice including the transparent conductor. Traditionally, a transparentconductor is formed as a coating of a doped metal oxide, such astin-doped indium oxide (or ITO), which is disposed on top of a glass orplastic film substrate. ITO coatings are typically formed through theuse of a dry process, such as through the use of specialized physicalvapor deposition (e.g., sputtering) or specialized chemical vapordeposition techniques. The resulting coating can exhibit goodtransparency and good electrical conductivity. However, drawbacks tosuch techniques include high cost, high process complexity, intensiveenergy requirements, high capital expenditures for equipment, and poorproductivity.

It is against this background that a need arose to develop thetransparent conductors and related manufacturing methods describedherein.

SUMMARY

One aspect of the invention relates to a transparent conductor. In oneembodiment, the transparent conductor includes: (1) a film of aconductive ceramic; and (2) conductive additives at least partiallyincorporated into the film and localized within a region of the film. Athickness of the region is less than an overall thickness of the film,and at least one of the conductive additives has an aspect ratio of atleast 3. The transparent conductor has a sheet resistance that is lessthan an intrinsic sheet resistance of the film.

Another aspect of the invention relates to a manufacturing method of atransparent conductor. In one embodiment, the method includes: (1)mixing conductive additives with a precursor of a conductive ceramic toform a mixture; (2) applying the mixture as a coating over a substrate;and (3) curing the coating to form a film of the conductive ceramic,where the conductive additives are at least partially incorporated intothe film.

In another embodiment, the method includes: (1) providing a precursor ofa conductive ceramic; (2) applying the precursor as a coating over asubstrate; (3) applying conductive additives to the coating to embed theconductive additives into the coating; and (4) curing the coating toform a film of the conductive ceramic, where the conductive additivesare at least partially embedded into the film.

In another embodiment, the method includes: (1) applying conductiveadditives over a substrate; (2) providing a precursor of a conductiveceramic; (3) applying the precursor as a coating over the conductiveadditives and the substrate; and (4) curing the coating to form a filmof the conductive ceramic, where the conductive additives are at leastpartially incorporated into the film.

Other aspects and embodiments of the invention are also contemplated.The foregoing summary and the following detailed description are notmeant to restrict the invention to any particular embodiment but aremerely meant to describe some embodiments of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

For a better understanding of the nature and objects of some embodimentsof the invention, reference should be made to the following detaileddescription taken in conjunction with the accompanying drawings.

FIG. 1A and FIG. 1B illustrate transparent conductors implemented inaccordance with embodiments of the invention.

FIG. 2A through FIG. 2C illustrate manufacturing methods to formtransparent conductors, according to embodiments of the invention.

FIG. 3A and FIG. 3B illustrate “under-embedding” and “over-embedding”scenarios, respectively, according to an embodiment of the invention.

FIG. 4 through FIG. 8 illustrate manufacturing methods to formtransparent conductors, according to embodiments of the invention.

FIG. 9 illustrates a LCD according to an embodiment of the invention.

FIG. 10 illustrates a color filter for use in an LCD according to anembodiment of the invention.

FIG. 11 illustrates thin-film solar cells according to an embodiment ofthe invention.

FIG. 12 illustrates a projected capacitive touch screen device accordingto an embodiment of the invention.

FIG. 13 illustrates an OLED lighting device according to an embodimentof the invention.

FIG. 14 illustrates an e-paper according to an embodiment of theinvention.

FIG. 15 illustrates a smart window according to an embodiment of theinvention.

FIG. 16 includes microscope images illustrating heat stability of atransparent conductor.

FIG. 17 includes microscope images illustrating heat stability of atransparent conductor.

DETAILED DESCRIPTION Definitions

The following definitions apply to some of the aspects described withregard to some embodiments of the invention. These definitions maylikewise be expanded upon herein.

As used herein, the singular terms “a,” “an,” and “the” include pluralreferents unless the context clearly dictates otherwise. Thus, forexample, reference to an object can include multiple objects unless thecontext clearly dictates otherwise.

As used herein, the term “set” refers to a collection of one or moreobjects. Thus, for example, a set of objects can include a single objector multiple objects. Objects of a set can also be referred to as membersof the set. Objects of a set can be the same or different. In someinstances, objects of a set can share one or more commoncharacteristics.

As used herein, the term “adjacent” refers to being near or adjoining.Adjacent objects can be spaced apart from one another or can be inactual or direct contact with one another. In some instances, adjacentobjects can be connected to one another or can be formed integrally withone another.

As used herein, the terms “connect,” “connected,” and “connection” referto an operational coupling or linking. Connected objects can be directlycoupled to one another or can be indirectly coupled to one another, suchas via another set of objects.

As used herein, the terms “substantially” and “substantial” refer to aconsiderable degree or extent. When used in conjunction with an event orcircumstance, the terms can refer to instances in which the event orcircumstance occurs precisely as well as instances in which the event orcircumstance occurs to a close approximation, such as accounting fortypical tolerance levels of the manufacturing methods described herein.

As used herein, the terms “optional” and “optionally” mean that thesubsequently described event or circumstance may or may not occur andthat the description includes instances where the event or circumstanceoccurs and instances in which it does not.

As used herein, relative terms, such as “inner,” “interior,” “outer,”“exterior,” “top,” “bottom,” “front,” “rear,” “back,” “upper,”“upwardly,” “lower,” “downwardly,” “vertical,” “vertically,” “lateral,”“laterally,” “above,” and “below,” refer to an orientation of a set ofobjects with respect to one another, such as in accordance with thedrawings, but do not require a particular orientation of those objectsduring manufacturing or use.

As used herein, the term “nanometer range” or “nm range” refers to arange of dimensions from about 1 nm to about 1 micrometer (“μm”). The nmrange includes the “lower nm range,” which refers to a range ofdimensions from about 1 nm to about 10 nm, the “middle nm range,” whichrefers to a range of dimensions from about 10 nm to about 100 nm, andthe “upper nm range,” which refers to a range of dimensions from about100 nm to about 1 μm.

As used herein, the term “micrometer range” or “μm range” refers to arange of dimensions from about 1 μm to about 1 millimeter (“mm”). The μmrange includes the “lower μm range,” which refers to a range ofdimensions from about 1 μm to about 10 μm, the “middle μm range,” whichrefers to a range of dimensions from about 10 μm to about 100 μm, andthe “upper μm range,” which refers to a range of dimensions from about100 μm to about 1 mm.

As used herein, the term “aspect ratio” refers to a ratio of a largestdimension or extent of an object and an average of remaining dimensionsor extents of the object, where the remaining dimensions are orthogonalwith respect to one another and with respect to the largest dimension.In some instances, remaining dimensions of an object can besubstantially the same, and an average of the remaining dimensions cansubstantially correspond to either of the remaining dimensions. Forexample, an aspect ratio of a cylinder refers to a ratio of a length ofthe cylinder and a cross-sectional diameter of the cylinder. As anotherexample, an aspect ratio of a spheroid refers to a ratio of a major axisof the spheroid and a minor axis of the spheroid.

As used herein, the term “nano-sized” object refers to an object thathas at least one dimension in the nm range. A nano-sized object can haveany of a wide variety of shapes, and can be formed of a wide variety ofmaterials. Examples of nano-sized objects include nanowires, nanotubes,nanoplatelets, nanoparticles, and other nanostructures.

As used herein, the term “nanowire” refers to an elongated, nano-sizedobject that is substantially solid. Typically, a nanowire has a lateraldimension (e.g., a cross-sectional dimension in the form of a width, adiameter, or a width or diameter that represents an average acrossorthogonal directions) in the nm range, a longitudinal dimension (e.g.,a length) in the μm range, and an aspect ratio that is about 3 orgreater.

As used herein, the term “nanoplatelet” refers to a planar-likenano-sized object that is substantially solid.

As used herein, the term “nanotube” refers to an elongated, hollow,nano-sized object. Typically, a nanotube has a lateral dimension (e.g.,a cross-sectional dimension in the form of a width, an outer diameter,or a width or outer diameter that represents an average acrossorthogonal directions) in the nm range, a longitudinal dimension (e.g.,a length) in the μm range, and an aspect ratio that is about 3 orgreater.

As used herein, the term “nanoparticle” refers to a spheroidal,nano-sized object. Typically, each dimension (e.g., a cross-sectionaldimension in the form of a width, a diameter, or a width or diameterthat represents an average across orthogonal directions) of ananoparticle is in the nm range, and the nanoparticle has an aspectratio that is less than about 3, such as about 1.

As used herein, the term “micron-sized” object refers to an object thathas at least one dimension in the μm range. Typically, each dimension ofa micron-sized object is in the μm range or beyond the μm range. Amicron-sized object can have any of a wide variety of shapes, and can beformed of a wide variety of materials. Examples of micron-sizedadditives include microwires, microtubes, microparticles, and othermicrostructures.

As used herein, the term “microwire” refers to an elongated,micron-sized object that is substantially solid. Typically, a microwirehas a lateral dimension (e.g., a cross-sectional dimension in the formof a width, a diameter, or a width or diameter that represents anaverage across orthogonal directions) in the μm range and an aspectratio that is about 3 or greater.

As used herein, the term “microtube” refers to an elongated, hollow,micron-sized object. Typically, a microtube has a lateral dimension(e.g., a cross-sectional dimension in the form of a width, an outerdiameter, or a width or outer diameter that represents an average acrossorthogonal directions) in the μm range and an aspect ratio that is about3 or greater.

As used herein, the term “microparticle” refers to a spheroidal,micron-sized object. Typically, each dimension (e.g., a cross-sectionaldimension in the form of a width, a diameter, or a width or diameterthat represents an average across orthogonal directions) of amicroparticle is in the μm range, and the microparticle has an aspectratio that is less than about 3, such as about 1.

As used herein, the term “ceramic” refers to an inorganic, non-metallicmaterial, which can be solid or solid-like. The term “ceramic”encompasses crystalline or partly crystalline materials as well asnon-crystalline or amorphous materials, such as glasses. The term“ceramic” encompasses, but is not limited to, materials such as oxides,such as alumina, silica, and titania, non-oxides, such as carbides,borides, and nitrides, and composite materials, such as particulatereinforced or fiber reinforced oxides, non-oxides or combinations ofoxides and non-oxides.

Transparent Conductors

Embodiments of the invention relate to electrically conductive orsemiconducting additives that are incorporated into host materials foruse as transparent conductors or other types of conductive structures.Embodiments of transparent conductors exhibit improved performance(e.g., higher electrical and thermal conductivity and higher lighttransmittance), as well as cost benefits arising from their structure,composition, and manufacturing process. In some embodiments, transparentconductors can be manufactured by a surface embedding process in whichadditives are physically embedded into a host material, while preservingdesired characteristics of the host material (e.g., transparency) andimparting additional desired characteristics to the resultingtransparent conductors (e.g., electrical conductivity). In otherembodiments, transparent conductors can be manufactured by bulkincorporation of additives into a host material, or by over-coatingadditives with a host material or a host material precursor. In otherembodiments, an over-coating can be a host material or a host materialprecursor.

One aspect of certain transparent conductors described herein is theprovision of a vertical additive concentration gradient or profile in ahost material, namely a gradient or profile along a thickness directionof the host material. Bulk incorporation within a substrate or a coatingaims to provide a relatively uniform vertical additive concentrationprofile throughout the substrate or the coating. In contrast, certaintransparent conductors described herein allow for variable, controllablevertical additive concentration profile, in accordance with alocalization of additives within an embedded region of a host material.For certain implementations, the extent of localization of additiveswithin an embedded region is such that at least a majority (by weight,volume, or number density) of the additives are included within theembedded region, such as at least about 60% (by weight, volume, ornumber density) of the additives are so included, at least about 70% (byweight, volume, or number density) of the additives are so included, atleast about 80% (by weight, volume, or number density) of the additivesare so included, at least about 90% (by weight, volume, or numberdensity) of the additives are so included, or at least about 95% (byweight, volume, or number density) of the additives are so included. Forexample, substantially all of the additives can be localized within theembedded region, such that a remainder of the host material issubstantially devoid of the additives. For certain applications, bulkincorporation can be used in place of, or in combination with,localization of additives within an embedded region.

Additives can be in the form of nano-sized additives, micron-sizedadditives, or a combination thereof. To impart electrical conductivity,additives can include an electrically conductive material, asemiconductor, or a combination thereof.

Additives also can be arranged in the form of structured or patternedgrids. For example, a grid of metal nanowires can be used, wherein eachwire in the grid is opaque (e.g. <10 μm, <5 μm, <1 μm), but because ofthe spacing between each wire, the transparency can still be high. Thesepatterned grids can be printed, etched, photographically developed,metallized, or by other techniques as well.

Examples of electrically conductive materials include metals (e.g.,silver, copper, and gold in the form of silver nanowires, coppernanowires, and gold nanowires), metal alloys, carbon-based conductors(e.g., in the form of carbon nanotubes, graphene, and buckyballs),conductive ceramics (e.g., conducting oxides and chalcogenides that areoptionally doped and transparent, such as metal oxides and chalcogenidesthat are optionally doped and transparent), electrically conductivepolymers (e.g., polyaniline, poly(acetylene), poly(pyrrole),poly(thiophene), poly(p-phenylene sulfide), poly(p-phenylene vinylene)(or PPV), poly(3-alkylthiophene), olyindole, polypyrene, polycarbazole,polyazulene, polyazepine, poly(fluorene), polynaphthalene, melanins,poly(3,4-ethylenedioxythiophene) (or PEDOT), poly(styrenesulfonate) (orPSS), PEDOT-PSS, PEDOT-polymethacrylic acid (or PEDOT-PMA),poly(3-hexylthiophene) (or P3HT), poly(3-octylthiophene) (or P3OT),poly(C-61-butyric acid-methyl ester) (or PCBM), andpoly[2-methoxy-5-(2′-ethyl-hexyloxy)-1,4-phenylene vinylene] (orMEH-PPV)), and any combination thereof. Further details regarding metaloxides and chalcogenides are set forth the sections below.

Examples of semiconductor materials include semiconducting polymers,Group IVB elements (e.g., carbon (or C), silicon (or Si), and germanium(or Ge)), Group IVB-IVB binary alloys (e.g., silicon carbide (or SiC)and silicon germanium (or SiGe)), Group IIB-VIB binary alloys (e.g.,cadmium selenide (or CdSe), cadmium sulfide (or CdS), cadmum telluride(or CdTe), zinc oxide (or ZnO), zinc selenide (or ZnSe), zinc telluride(or ZnTe), and zinc sulfide (or ZnS)), Group IIB-VIB ternary alloys(e.g., cadmium zinc telluride (or CdZnTe), mercury cadmium telluride (orHgCdTe), mercury zinc telluride (or HgZnTe), and mercury zinc selenide(or HgZnSe)), Group IIIB-VB binary alloys (e.g., aluminum antimonide (orAlSb), aluminum arsenide (or AlAs), aluminium nitride (or MN), aluminiumphosphide (or AlP), boron nitride (or BN), boron phosphide (or BP),boron arsenide (or BAs), gallium antimonide (or GaSb), gallium arsenide(or GaAs), gallium nitride (or GaN), gallium phosphide (or GaP), indiumantimonide (or InSb), indium arsenide (or InAs), indium nitride (orInN), and indium phosphide (or InP)), Group IIIB-VB ternary alloys(e.g., aluminium gallium arsenide (or AlGaAs or Al_(x)Ga_(1-x)As),indium gallium arsenide (or InGaAs or In_(x)Ga_(1-x)As), indium galliumphosphide (or InGaP), aluminium indium arsenide (or AlinAs), aluminiumindium antimonide (or AlInSb), gallium arsenide nitride (or GaAsN),gallium arsenide phosphide (or GaAsP), aluminium gallium nitride (orAlGaN), aluminium gallium phosphide (or AlGaP), indium gallium nitride(or InGaN), indium arsenide antimonide (or InAsSb), and indium galliumantimonide (or InGaSb)), Group IIIB-VB quaternary alloys (e.g.,aluminium gallium indium phosphide (or AlGaInP), aluminium galliumarsenide phosphide (or AlGaAsP), indium gallium arsenide phosphide (orInGaAsP), aluminium indium arsenide phosphide (or AlInAsP), aluminiumgallium arsenide nitride (or AlGaAsN), indium gallium arsenide nitride(or InGaAsN), indium aluminium arsenide nitride (or InAlAsN), andgallium arsenide antimonide nitride (or GaAsSbN)), and Group IIIB-VBquinary alloys (e.g., gallium indium nitride arsenide antimonide (orGaInNAsSb) and gallium indium arsenide antimonide phosphide (orGaInAsSbP)), Group IB-VIIB binary alloys (e.g., cupruous chloride (orCuCl)), Group IVB-VIB binary alloys (e.g., lead selenide (or PbSe), leadsulfide (or PbS), lead telluride (or PbTe), tin sulfide (or SnS), andtin telluride (or SnTe)), Group IVB-VIB ternary alloys (e.g., lead tintelluride (or PbSnTe), thallium tin telluride (or Tl₂SnTe₅), andthallium germanium telluride (or Tl₂GeTe₅)), Group VB-VIB binary alloys(e.g., bismith telluride (or Bi₂Te₃)), Group IIB-VB binary alloys (e.g.,cadmium phosphide (or Cd₃P₂), cadmium arsenide (or Cd₃As₂), cadmiumantimonide (or Cd₃Sb₂), zinc phosphide (or Zn₃P₂), zinc arsenide (orZn₃As₂), and zinc antimonide (or Zn₃Sb₂)), and other binary, ternary,quaternary, or higher order alloys of Group IB (or Group 11) elements,Group IIB (or Group 12) elements, Group IIIB (or Group 13) elements,Group IVB (or Group 14) elements, Group VB (or Group 15) elements, GroupVIB (or Group 16) elements, and Group VIIB (or Group 17) elements, suchas copper indium gallium selenide (or CIGS), as well as any combinationthereof.

Additives can include, for example, metallic or semiconductingnanoparticles, nanowires (e.g. silver, copper, or zinc), nanoplates,nanoflakes, nanofibers, nanorods, nanotubes (e.g., carbon nanotubes,multi-walled nanotubes (“MWNTs”), single-walled nanotubes (“SWNTs”),double-walled nanotubes (“DWNTs”), graphitized or modified nanotubes),fullerenes, buckyballs, graphene, microparticles, microwires,microtubes, core-shell nanoparticles or microparticles, core-multishellnanoparticles or microparticles, core-shell nanowires, and otheradditives having shapes that are substantially tubular, cubic,spherical, or pyramidal, and characterized as amorphous, crystalline,tetragonal, hexagonal, trigonal, orthorhombic, monoclinic, or triclinic,or any combination thereof.

Examples of core-shell nanoparticles and core-shell nanowires includethose with a ferromagnetic core (e.g., iron, cobalt, nickel, manganese,as well as their oxides and alloys formed with one or more of theseelements), with a shell formed of a metal, a metal alloy, a metal oxide,carbon, or any combination thereof (e.g., silver, copper, gold,platinum, a conducting oxide or chalcogenide, graphene, and othermaterials listed as suitable additives herein). A particular example ofa core-shell nanowire is one with a silver core and a gold shell (or aplatinum shell or another type of shell) surrounding the silver core toreduce or prevent oxidation of the silver core. Another example of acore-shell nanowire is one with a silver core (or a core formed ofanother metal or other electrically conductive material), with a shellor other coating formed of one or more of the following: (a) conductingpolymers, such as poly(3,4-ethylenedioxythiophene) (or PEDOT) andpolyaniline (or PANI); (b) conducting oxides, chalcogenides, andceramics (e.g., deposited by sol-gel, chemical vapor deposition,physical vapor deposition, plasma-enhanced chemical vapor deposition, orchemical bath deposition); (c) insulators in the form of ultra-thinlayers, such as polymers, SiO₂, BaTiO, and TiO₂; and (d) thin layers ofmetals, such as gold, copper, nickel, chromium, molybdenum, andtungsten. Such coated or core-shell form of nanowires can be desirableto impart electrical conductivity, while avoiding or reducing adverseinteractions with a host material, such as potential yellowing or otherdiscoloration in the presence of a metal such as silver, oxidation(e.g., a silver/gold core/shell nanowires can have substantially loweroxidation due to the gold shell), and sulfidation (e.g., asilver/platinum core/shell nanowire can have substantially lowersulfidation due to the platinum shell).

For certain implementations, high aspect ratio additives are desirable,such as in the form of nanowires, nanotubes, and combinations thereof.For example, desirable additives include nanotubes formed of carbon orother materials (e.g., MWNTs, SWNTs, graphitized MWNTs, graphitizedSWNTs, modified MWNTs, modified SWNTs, and polymer-containingnanotubes), nanowires formed of a metal, a metal oxide, a metal alloy,or other materials (e.g., silver nanowires, copper nanowires, zinc oxidenanowires (undoped or doped by, for example, aluminum, boron, fluorine,and others), tin oxide nanowires (undoped or doped by, for example,fluorine), cadmium tin oxide nanowires, ITO nanowires,polymer-containing nanowires, and gold nanowires), as well as othermaterials that are electrically conductive or semiconducting and havinga variety of shapes, whether cylindrical, spherical, pyramidal, orotherwise. Additional examples of additives include those formed ofactivated carbon, graphene, carbon black, ketjen black, andnanoparticles formed of a metal, a metal oxide, a metal alloy, or othermaterials (e.g., silver nanoparticles, copper nanoparticles, zinc oxidenanoparticles, ITO nanoparticles, and gold nanoparticles).

A host material can have a variety of shapes and sizes, can betransparent, translucent, or opaque, can be flexible, bendable, foldableor rigid, can be electromagnetically opaque or electromagneticallytransparent, and can be electrically conductive, semiconducting, orinsulating. The host material can be in the form of a layer, a film, ora sheet serving as a substrate, or can be in the form of a coating ormultiple coatings disposed on top of a substrate or another material.Examples of suitable host materials include ceramics, such as dielectricor non-conductive ceramics (e.g., SiO₂-based glass; SiO_(x)-based glass;TiO_(x)-based glass; other titanium, cerium, magnesium analogues ofSiO_(x)-based glass; spin-on glass; glass formed from sol-gelprocessing, silane precursor, siloxane precursor, silicate precursor,tetraethyl orthosilicate, silane, siloxane, phosphosilicates, spin-onglass, silicates, sodium silicate, potassium silicate, a glassprecursor, a ceramic precursor, silsesquioxane, metallasilsesquioxanes,polyhedral oligomeric silsesquioxanes, halosilane, sol-gel,silicon-oxygen hydrides, silicones, stannoxanes, silathianes, silazanes,polysilazanes, metallocene, titanocene dichloride, vanadocenedichloride; and other types of glasses), conductive ceramics (e.g.,conducting oxides and chalcogenides that are optionally doped andtransparent, such as metal oxides and chalcogenides that are optionallydoped and transparent), and any combination thereof. Additional examplesof suitable host materials include electrically conductive materials andsemiconductors listed above as suitable materials for additives. Thehost material can be, for example, n-doped, p-doped, or un-doped.Further details regarding metal oxides and chalcogenides are set forththe sections below.

In some embodiments, confining additives to a “planar” or “planar-like”embedded region of a host material can lead to decreased topologicaldisorder of the additives and increased occurrence of junction formationbetween the additives for improved electrical conductivity. Although anembedded region is sometimes referred as “planar,” it will be understoodthat such embedded region is typically not strictly two-dimensional, asthe additives themselves are typically three-dimensional. Rather,“planar” can be used in a relative sense, with a relatively thin,slab-like (or layered) local concentration of the additives within acertain region of the host material, and with the additives largelyabsent from a remainder of the host material. It is noted that the localconcentration of additives can be non-planar in the sense that it can benon-flat. For example, the additives can be concentrated in a thinregion of the host material that is characterized by curvature withrespect to one or more axes, with the additives largely absent from aremainder of the host material. It will also be understood that anembedded region can be referred as “planar,” even though such anembedded region can have a thickness that is greater than (e.g., severaltimes greater than) a characteristic dimension of additives. In general,an embedded region can be located adjacent to a side of a host material,adjacent to a middle of the host material, or adjacent to any arbitrarylocation along a thickness direction of the host material, and multipleembedded regions can be located adjacent to one another or spaced apartfrom one another within the host material. Each embedded region caninclude one or more types of additives, and embedded regions (which arelocated in the same host material) can include different types ofadditives. In some embodiments, by confining electrically conductiveadditives to a set of “planar” embedded regions of a host material (asopposed to randomly throughout the host material), a higher electricalconductivity can be achieved for a given amount of the additives perunit of area. Any additives not confined to an embedded region representan excess amount of additives that can be omitted.

In some embodiments, transparent conductors can have additives embeddedor otherwise incorporated into a host material from about 10% (or less,such as from about 0.1%) by volume into an embedding surface and up toabout 100% by volume into the embedding surface, and can have theadditives exposed at varying surface area coverage, such as from about0.1% surface area coverage (or less, such as 0% when an embedded regionis entirely below the surface, or when the additives are completelyencapsulated by the host material) up to about 99.9% (or more) surfacearea coverage. For example, in terms of a volume of an additive embeddedbelow the embedding surface relative to a total volume of the additive,at least one additive can have an embedded volume percentage (or apopulation of the additives can have an average embedded volumepercentage) in the range of about 0% to about 100%, such as from 10% toabout 50%, or from about 50% to about 100%.

Transparent conductors of some embodiments can have an embedded regionwith a thickness greater than a characteristic dimension of additivesused (e.g., for nanowires, greater than a diameter of an individualnanowire or an average diameter across the nanowires), with theadditives largely confined to the embedded region with the thicknessless than an overall thickness of the host material. For example, thethickness of the embedded region can be no greater than about 80% of theoverall thickness of the host material, such as no greater than about50%, no greater than about 40%, no greater than about 30%, no greaterthan about 20%, no greater than about 10%, or no greater than about 5%of the overall thickness. In other embodiments, additives can bedistributed throughout a larger volume fraction within a host material,such as in the case of bulk incorporation.

In some embodiments, additives can be embedded or otherwise incorporatedinto a host material by varying degrees relative to a characteristicdimension of the additives used (e.g., for nanowires, relative to adiameter of an individual nanowire or an average diameter across thenanowires). For example, in terms of a distance of a furthest embeddedpoint on an additive below an embedding surface, at least one additivecan be embedded to an extent of more than about 100% of thecharacteristic dimension, or can be embedded to an extent of not morethan about 100% of the characteristic dimension, such as at least about5% or about 10% and up to about 80%, up to about 50%, or up to about 25%of the characteristic dimension. As another example, a population of theadditives, on average, can be embedded to an extent of more than about100% of the characteristic dimension, or can be embedded to an extent ofnot more than about 100% of the characteristic dimension, such as atleast about 5% or about 10% and up to about 80%, up to about 50%, or upto about 25% of the characteristic dimension. As will be understood, theextent to which additives are embedded into a host material can impact aroughness of an embedding surface, such as when measured as an extent ofvariation of heights across the embedding surface (e.g., a standarddeviation relative to an average height). In some embodiments, aroughness of the surface-embedded structure is less than acharacteristic dimension of partially embedded additives.

In some embodiments, at least one additive can extend out from anembedding surface of a host material from about 0.1 nm to about 1 cm,such as from about 1 nm to about 50 nm, from about 50 nm to 100 nm, orfrom about 100 nm to about 100 microns. In other embodiments, apopulation of additives, on average, can extend out from an embeddingsurface of a host material from about 0.1 nm to about 1 cm, such as fromabout 1 nm to about 50 nm, from about 50 nm to 100 nm, or from about 100nm to about 100 microns. In other embodiments, substantially all of asurface area of a host material (e.g., an area of an embedding surface)is occupied by additives. In other embodiments, up to about 100% or upto about 75% of the surface area is occupied by additives, such as up toabout 50% of the surface area, up to about 25% of the surface area, upto about 10%, up to about 5%, up to about than 3% of the surface area,or up to about 1% of the surface area is occupied by additives.Additives need not extend out from an embedding surface of a hostmaterial, and can be localized entirely below the embedding surface Thedegree of embedding and surface coverage of additives for asurface-embedded structure can be selected in accordance with aparticular application.

In some embodiments, if nanowires are used as additives, characteristicsthat can influence electrical conductivity and other desirablecharacteristics include, for example, nanowire density or loading level,surface area coverage, nanowire length, nanowire diameter, uniformity ofthe nanowires, material type, stability of the nanowire formulations,wire-wire junction resistance, host-material resistance, nanowireconductivity, crystallinity of the nanowire, and purity. There can be apreference for nanowires with a low junction resistance and a low bulkresistance in some embodiments. For attaining higher electricalconductivity while maintaining high transparency, thinner diameter,longer length nanowires can be used (e.g., with relatively large aspectratios to facilitate nanowire junction formation and in the range ofabout 50 to about 2,000, such as from about 50 to about 1,000, or fromabout 100 to about 800), and metallic nanowires, such as silver, copper,and gold nanowires, can be used. In other embodiments, if the nanowiresare thin, their bulk conductivity can decrease because of the smallcross-sectional area of the wires; therefore, in some embodiments,thicker diameter wires can be selected. Using nanowires as additives toform nanowire networks, such as silver nanowire networks, can bedesirable for some embodiments. Other metallic nanowires, non-metallicnanowires, such as ITO and other oxide and chalcogenide nanowires, alsocan be used. Additives composed of semiconductors with bandgaps outsidethe visible optical spectrum energies (e.g., <1.8 eV and >3.1 eV) orapproximately near this range, can be used to create transparentconductors with high optical transparency in that visible light willtypically not be absorbed by the bandgap energies or by interfacialtraps therein. Various dopants can be used to tune the conductivity ofthese aforementioned semiconductors, taking into account the shiftedFermi levels and bandgap edges via the Moss-Burstein effect. Thenanowires can be largely uniform or monodisperse in terms of dimensions(e.g., diameter and length), such as the same within about 5% (e.g., astandard deviation relative to an average diameter or length), the samewithin about 10%, the same within about 15%, or the same within about20%. Purity can be, for example, at least about 50%, at least about 75%,at least about 85%, at least about 90%, at least about 95%, at leastabout 99%, at least about 99.9%, or at least about 99.99%. Surface areacoverage of nanowires can be, for example, up to about 100%, less thanabout 100%, up to about 75%, up to about 50%, up to about 25%, up toabout 10%, up to about 5%, up to about 3%, or up to about 1%. Silvernanowires can be particularly desirable for certain embodiments, sincesilver oxide, which can form (or can be formed) on surfaces of thenanowires as a result of oxidation, is electrically conductive. Also,core-shell nanowires (e.g., silver core with gold or platinum shell)also can decrease junction resistance.

In some embodiments, if nanotubes are used as additives (whether formedof carbon, a metal, a metal alloy, a metal oxide, or another material),characteristics that can influence electrical conductivity and otherdesirable characteristics include, for example, nanotube density orloading level, surface area coverage, nanotube length, nanotube innerdiameter, nanotube outer diameter, whether single-walled or multi-wallednanotubes are used, uniformity of the nanotubes, material type, andpurity. There can be a preference for nanotubes with a low junctionresistance in some embodiments. For reduced scattering in the context ofcertain devices such as displays, nanotubes, such as carbon nanotubes,can be used to form nanotube networks. Alternatively, or in combination,smaller diameter nanowires can be used to achieve a similar reduction inscattering relative to the use of nanotubes. Nanotubes can be largelyuniform or monodisperse in terms of dimensions (e.g., outer diameter,inner diameter, and length), such as the same within about 5% (e.g., astandard deviation relative to an average outer/inner diameter orlength), the same within about 10%, the same within about 15%, or thesame within about 20%. Purity can be, for example, at least about 50%,at least about 75%, at least about 85%, at least about 90%, at leastabout 95%, at least about 99%, at least about 99.9%, or at least about99.99%. Surface area coverage of nanotubes can be, for example, up toabout 100%, less than about 100%, up to about 75%, up to about 50%, upto about 25%, up to about 10%, up to about 5%, up to about 3%, or up toabout 1%.

It should be understood that the number of additive types can be variedfor a given device or application. For example, any, or a combination,of silver nanowires, copper nanowires, and gold nanowires can be usedalong with ITO nanoparticles to yield high optical transparency and highelectrical conductivity. Similar combinations include, for example, any,or a combination, of silver nanowires, copper nanowires, and goldnanowires along with any one or more of ITO nanowires, ZnO nanowires,ZnO nanoparticles, silver nanoparticles, gold nanoparticles, SWNTs,MWNTs, fullerene-based materials (e.g., carbon nanotubes andbuckyballs), and ITO nanoparticles. The use of ITO nanoparticles,nanowires, or layers of conductive oxides or ceramics (e.g., ITO,aluminum-doped zinc oxide, or other types of doped or undoped zincoxides) can provide additional functionality, such as by serving as abuffer layer to adjust a work function in the context of function of atransparent electrode for use in a solar device, a thin-film solardevice, an OLED display type device, an OLED lighting type device, orsimilar device to provide a conductive path for the flow of an electriccurrent, in place of, or in combination with, a conductive path providedby other additives.

In some embodiments, additives are initially provided as discreteobjects. Upon embedding or incorporation into a host material, the hostmaterial can envelop or surround the additives such that the additivesbecome aligned or otherwise arranged within a “planar” or “planar-like”embedded region. In some embodiments for the case of additives such asnanowires, nanotubes, microwires, microtubes, or other additives with anaspect ratio greater than 1, the additives become aligned such thattheir lengthwise or longitudinal axes are largely confined to within arange of angles relative to a horizontal plane, or another planecorresponding, or parallel, to a plane of an embedding surface. Forexample, the additives can be elongated and can be aligned such thattheir lengthwise or longest-dimension axes, on average, are confined toa range from about −45° to about +45° relative to the horizontal plane,such as from about −35° to about +35°, from about −25° to about +25°,from about −15° to about +15°, from about −5° to about +5°, from about−1° to about +1°, from about −0.1° to about +0.1°, or from about −0.01°to about +0.01°. Stated in another way, lengthwise axes of the additivescan be confined such that θ<SIN⁻¹(t/L), where L=length of an additive,t=thickness of the host material, and θ is an angle relative to ahorizontal plane corresponding to the embedding surface. In thisexample, little or substantially none of the additives can have theirlengthwise or longitudinal axes oriented outside of the range from about−45° to about +45° relative to the horizontal plane. Within the embeddedregion, neighboring additives can contact one another in someembodiments. Such contact can be improved using longer aspect ratioadditives, while maintaining a relatively low surface area coverage fordesired transparency. In some embodiments, contact between additives,such as nanowires, nanoparticles, microwires, and microparticles, can beincreased through sintering or annealing, such as low temperaturesintering at temperatures of about 50° C., about 125° C., about 150° C.,about 175° C., or about 200° C., or in the range of about 50° C. toabout 125° C., about 100° C. to about 125° C., about 125° C. to about150° C., about 150° C. to about 175° C., or about 175° C. to about 200°C., flash sintering, sintering through the use of redox reactions tocause deposits onto additives to grow and fuse the additives together,or any combination thereof. For example, in the case of silver or goldadditives, silver ions or gold ions can be deposited onto the additivesto cause the additives to fuse with neighboring additives. Hightemperature sintering at temperatures at or above about 200° C. is alsocontemplated. It is also contemplated that little or no contact isneeded for certain applications and devices, where charge tunneling orhopping provides sufficient electrical conductivity in the absence ofactual contact, or where a host material or a coating on top of the hostmaterial may itself be electrically conductive or semiconducting. Suchapplications and devices can operate with a sheet resistance up to about10⁶ Ω/sq or more. Individual additives can be separated by electricaland quantum barriers for electron transfer.

Transparent conductors described herein can be quite durable. In someembodiments, such durability is in combination with rigidity androbustness, and, in other embodiments, such durability is in combinationwith the ability to be flexed, rolled, bent, and folded, amongst otherphysical actions, with, for example, no greater than about 50%, nogreater than about 40%, no greater than about 30%, no greater than about20%, no greater than about 15%, no greater than about 10%, no greaterthan about 5%, no greater than about 3%, or substantially no decrease intransmittance, and no greater than about 50%, no greater than about 40%,no greater than about 30%, no greater than about 20%, no greater thanabout 15%, no greater than about 10%, no greater than about 5%, nogreater than about 3%, or substantially no increase in resistance (e.g.,sheet resistance). In some embodiments, the transparent conductors cansurvive a standard test for adhesion of coatings (e.g., a Scotch TapeTest) used in the coatings industry and yield substantially no decrease,or no greater than about 5% decrease, no greater than about 10%decrease, no greater than about 15% decrease, no greater than about 20%decrease, no greater than about 30% decrease, no greater than about 40%decrease, or no greater than about 50% decrease in observedtransmittance, and yield substantially no increase, or no greater thanabout 5% increase, no greater than about 10% increase, no greater thanabout 15% increase, no greater than about 20% increase, no greater thanabout 30% increase, no greater than about 40% increase, or no greaterthan about 50% increase in observed resistance (e.g., sheet resistance).In some embodiments, the transparent conductors can also surviverubbing, scratching, flexing, physical abrasion, thermal cycling (e.g.,exposure to temperatures up to (or at least) about 600° C., up to (or atleast) about 550° C., up to (or at least) about 500° C., up to (or atleast) about 450° C., or up to (or at least) about 400° C.), chemicalexposure, accelerated life test (“ALT”), and humidity cycling withsubstantially no decrease, no greater than about 50% decrease, nogreater than about 40% decrease, no greater than about 30% decrease, nogreater than about 20% decrease, no greater than about 15% decrease, nogreater than about 10% decrease, no greater than about 5% decrease, orno greater than about 3% decrease in observed transmittance, and withsubstantially no increase, no greater than about 50% increase, nogreater than about 40% increase, no greater than about 30% increase, nogreater than about 20% increase, no greater than about 15% increase, nogreater than about 10% increase, no greater than about 5% increase, orno greater than about 3% increase in observed resistance (e.g., sheetresistance). This enhanced durability can result from embedding orincorporation of additives within a host material, such that theadditives are physically or chemically held inside the host material bymolecular chains or other components of the host material. In somecases, flexing or pressing can be observed to increase conductivity.

Various standard tests can be used to measure durability, such as interms of abrasion resistance. One such test, among others, isASTM-F735-06 Standard Test Method for Abrasion Resistance of TransparentPlastics and Coatings Using the Oscillating Sand Method. Another testthat can be used is ASTM D1044-08 Standard Test Method for Resistance ofTransparent Plastics to Surface Abrasion. Yet another possible standardtest is ASTM D4060-10 Standard Test Method for Abrasion Resistance ofOrganic Coatings by the Taber Abraser. Additional standard tests thatcan be used include tests for hardness, such as ASTM D3363-05 (2011)e1Standard Test Method for Film Hardness by Pencil Test, ASTM E384, ASTME10, ASTM B277-95 Standard Test Method for Hardness of ElectricalContact Materials, and ASTM D2583-06 Standard Test Method forIndentation Hardness of Rigid Plastics by Means of a Barcol Impressor.Further details on these tests are available from ASTM International ofWest Conshohocken, Pa. Other standardized protocols include the ISO15184, JIS K-5600, ECCA-T4-1, BS 3900-E19, SNV 37113, SIS 184187, NCN5350, and MIL C 27 227.

Another set of tests can be used to measure and evaluate reliabilityunder ALT conditions. Some industry standards include dry heat (e.g.,85° C./dry), moist heat (e.g., 60° C./90% RH, or 85° C./85° RH), drycold (e.g., −30° C./dry), thermal shock (e.g., 80° C.←→40° C. cycle for30 minutes each). These ALT conditions can be carried out over hours,days, weeks, or months with samples exposed to those conditions forextended periods of time or number of cycles. In certain embodiments ofthe transparent conductors disclosed herein, the change in sheetresistance, transparency, and/or haze are controlled within +/−50%, inother cases, +/−25%, in other cases, +/−10%, and in other cases, +/−5%,or lower.

Another aspect of some embodiments of transparent conductors is that anelectrical percolation threshold can be attained using a lesser amountof additives. Stated in another way, electrical conductivity can beattained using less additive material, thereby saving additive materialand associated cost and increasing transparency. As will be understood,an electrical percolation threshold is typically reached when asufficient amount of additives is present to allow percolation ofelectrical charge from one additive to another additive, therebyproviding a conductive path across at least portion of a network ofadditives. In some embodiments, an electrical percolation threshold canbe observed via a change in slope of a logarithmic plot of resistanceversus loading level of additives. A lesser amount of additive materialcan be used since additives are largely confined to a “planar” or“planar-like” embedded region in some embodiments, thereby greatlyreducing topological disorder and resulting in a higher probability ofinter-additive (e.g., inter-nanowire or inter-nanotube) junctionformation. In other words, because the additives are confined to a thinembedded region in the host material, as opposed to dispersed throughoutthe thickness of the host material, the probability that the additiveswill interconnect and form junctions can be greatly increased. A lesseramount of additive material also can be used in embodiments where a hostmaterial is itself electrically conductive or semiconducting. In someembodiments, an electrical percolation threshold can be attained at aloading level of additives in the range of about 0.001 μg/cm² to about100 μg/cm² (or higher), such as from about 0.01 μg/cm² to about 100μg/cm², from about 10 μg/cm² to about 100 μg/cm², from 0.01 μg/cm² toabout 0.4 μg/cm², from about 0.5 μg/cm² to about 5 μg/cm², or from about0.8 μg/cm² to about 3 μg/cm² for certain additives such as silvernanowires. These loading levels can be varied according to dimensions,material type, spatial dispersion, and other characteristics ofadditives.

In addition, a lesser amount of additives can be used (e.g., asevidenced by a thickness of an embedded region) to achieve anetwork-to-bulk transition, which is a parameter representing atransition of a thin layer from exhibiting effective material propertiesof a sparse two-dimensional conducting network to one exhibitingeffective properties of a three-dimensional conducting bulk material. Byconfining additives to a “planar” or “planar-like” embedded region, alower sheet resistance can be attained at specific levels of solarflux-weighted transmittance. Furthermore, in some embodiments, carrierrecombination can be reduced due to the reduction or elimination ofinterfacial defects associated with a separate coating or othersecondary material into which additives are mixed.

To expound further on these advantages, a network of additives can becharacterized by a topological disorder and by contact resistance.Topologically, above a critical density of additives and above acritical density of additive-additive (e.g., nanowire-nanowire,nanotube-nanotube, or nanotube-nanowire) junctions, electrical currentcan readily flow from a source to a drain. A “planar” or “planar-like”network of additives can reach a network-to-bulk transition with areduced thickness, represented in terms of a characteristic dimension ofthe additives (e.g., for nanowires, relative to a diameter of anindividual nanowire or an average diameter across the nanowires). Forexample, an embedded region can have a thickness up to about 10 times(or more) the characteristic dimension, such as up to about 9 times, upto about 8 times, up to about 7 times, up to about 6 times, up to about5 times, up to about 4 times, up to about 3 times, or up to about 2times the characteristic dimension, and down to about 0.05, about 0.1,about 0.2, about 0.3, about 0.4, or about 0.5 times the characteristicdimension, allowing devices to be thinner while increasing opticaltransparency and electrical conductivity. Accordingly, the transparentconductors described herein provide, in some embodiments, an embeddedregion with a thickness up to about n×d (in terms of nm) within whichare localized additives having a characteristic dimension of d (in termsof nm), where n=2, 3, 4, 5, or higher.

Another advantage of some embodiments of transparent conductors is that,for a given level of electrical conductivity, the transparent conductorscan yield higher transparency. This is because less additive materialcan be used to attain that level of electrical conductivity, in view ofthe efficient formation of additive-additive junctions for a givenloading level of additives, in view of the use of a host material thatis itself electrically conductive or semiconducting, or both. As will beunderstood, a transmittance of a thin conducting material (e.g., in theform of a film) can be expressed as a function of its sheet resistanceR_(□) and an optical wavelength, as given by the following approximaterelation for a thin film:

${T(\lambda)} = \left( {1 + {\frac{188.5}{R_{\square}}\frac{\sigma_{op}(\lambda)}{\sigma_{DC}}}} \right)^{- 2}$

where σ_(Op) and σ_(DC) are the optical and DC conductivities of thematerial, respectively. In some embodiments, silver nanowire networkssurface-embedded or otherwise incorporated into flexible transparentsubstrates can have sheet resistances as low as about 3.2 Ω/sq or about0.2 Ω/sq, or even lower. In other embodiments, transparent conductorssuitable for solar devices can reach up to about 85% (or more) for solarflux-weighted transmittance T_(solar) and a sheet resistances as low asabout 20 Ω/sq (or below). In still other embodiments, a sheet resistanceof ≦10 Ω/sq at ≧85% (e.g., at least about 85%, at least about 90%, or atleast about 95%, and up to about 97%, about 98%, or more) solarflux-weighted transmittance can be obtained with the transparentconductors. It will be understood that transmittance can be measuredrelative to other ranges of optical wavelength, such as transmittance ata given wavelength of 550 nm, a human vision or photometric-weightedtransmittance (e.g., from about 350 nm to about 700 nm), solar-fluxweighted transmittance, transmittance at a given wavelength or range ofwavelengths in the infrared range, and transmittance at a givenwavelength or range of wavelengths in the ultraviolet range. It willalso be understood that transmittance can be measured relative to asubstrate (if present) (e.g., the transmittance valued would not includethe transmittance loss from an underlying substrate that is below a hostmaterial that includes additives), or can be measured relative to air(e.g., the transmittance value would include the transmittance loss froman underlying substrate). Unless otherwise specified herein,transmittance values are designated relative to a substrate (ifpresent), although similar transmittance values (albeit with somewhathigher values) are also contemplated when measured relative to air. Forsome embodiments, a DC-to-optical conductivity ratio of surface-embeddedstructures can be at least about 100, at least about 115, at least about300, at least about 400, or at least about 500, and up to about 600, upto about 800, or more.

Certain transparent conductors can include additives of nanowires (e.g.,silver nanowires) of average diameter in the range of about 1 nm toabout 100 nm, about 10 nm to about 80 nm, about 20 nm to about 80 nm, orabout 40 nm to about 60 nm, and an average length in the range of about50 nm to about 1,000 μm, about 50 nm to about 500 μm, about 100 nm toabout 100 μm, about 500 nm to 50 μm, about 5 μm to about 50 μm, about 20μm to about 150 μm, about 5 μm to about 35 μm, about 25 μm to about 80μm, about 25 μm to about 50 μm, or about 25 μm to about 40 μm. A top ofan embedded region can be located about 0 nm to about 100 μm below atop, embedding surface of a host material, such as about 0.0001 nm toabout 100 μm below the embedding surface, about 0.01 nm to about 100 μmbelow the embedding surface, about 0.1 nm to 100 μm below the embeddingsurface, about 0.1 nm to about 5 μm below the embedding surface, about0.1 nm to about 3 μm below the embedding surface, about 0.1 nm to about1 μm below the embedding surface, or about 0.1 nm to about 500 nm belowthe embedding surface. Nanowires embedded or incorporated into a hostmaterial can protrude from an embedding surface from about 0% by volumeand up to about 90%, up to about 95%, or up to about 99% by volume. Forexample, in terms of a volume of a nanowire exposed above the embeddingsurface relative to a total volume of the nanowire, at least onenanowire can have an exposed volume percentage (or a population of thenanowires can have an average exposed volume percentage) of up to about1%, up to about 5%, up to about 20%, up to about 50%, or up to about 75%or about 95%. At a transmittance of about 85% or greater (e.g., solarflux-weighted transmittance or one measured at another range of opticalwavelengths), a sheet resistance can be no greater than about 500 Ω/sq,no greater than about 400 Ω/sq, no greater than about 350 Ω/sq, nogreater than about 300 Ω/sq, no greater than about 200 Ω/sq, no greaterthan about 100 Ω/sq, no greater than about 75 Ω/sq, no greater thanabout 50 Ω/sq, no greater than about 25 Ω/sq, no greater than about 20Ω/sq, no greater than about 15 Ω/sq, no greater than about 10 Ω/sq, anddown to about 1 Ω/sq or about 0.1 Ω/sq, or less. At a transmittance ofabout 90% or greater, a sheet resistance can be no greater than about500 Ω/sq, no greater than about 400 Ω/sq, no greater than about 350Ω/sq, no greater than about 300 Ω/sq, no greater than about 200 Ω/sq, nogreater than about 100 Ω/sq, no greater than about 75 Ω/sq, no greaterthan about 50 Ω/sq, no greater than about 25 Ω/sq, no greater than about20 Ω/sq, no greater than about 15 Ω/sq, no greater than about 10 Ω/sq,and down to about 1 Ω/sq or less.

Certain transparent conductors can include additives of nanotubes (e.g.,either, or both, MWCNT and SWCNT) of average outer diameter in the rangeof about 1 nm to about 100 nm, about 1 nm to about 10 nm, about 10 nm toabout 50 nm, about 10 nm to about 80 nm, about 20 nm to about 80 nm, orabout 40 nm to about 60 nm, and an average length in the range of about50 nm to about 100 nm, about 100 nm to about 100 nm, about 500 nm to 50nm, about 5 μm to about 50 nm, about 5 μm to about 35 nm, about 25 μm toabout 80 nm, about 25 μm to about 50 nm, or about 25 μm to about 40 nm.A top of an embedded region can be located about 0 nm to about 100 μmbelow a top, embedding surface of a host material, such as about 0.01 nmto about 100 μm below the embedding surface, about 0.1 nm to 100 μmbelow the embedding surface, about 0.1 nm to about 5 μm below theembedding surface, about 0.1 nm to about 3 μm below the embeddingsurface, about 0.1 nm to about 1 μm below the embedding surface, orabout 0.1 nm to about 500 nm below the embedding surface. Nanotubesembedded or incorporated into a host material can protrude from anembedding surface from about 0% by volume and up to about 90%, up toabout 95%, or up to about 99% by volume. For example, in terms of avolume of a nanotube exposed above the embedding surface relative to atotal volume of the nanotube (e.g., as defined relative to an outerdiameter of a nanotube), at least one nanotube can have an exposedvolume percentage (or a population of the nanotubes can have an averageexposed volume percentage) of up to about 1%, up to about 5%, up toabout 20%, up to about 50%, or up to about 75% or about 95%. At atransmittance of about 85% or greater (e.g., solar flux-weightedtransmittance or one measured at another range of optical wavelengths),a sheet resistance can be no greater than about 500 Ω/sq, no greaterthan about 400 Ω/sq, no greater than about 350 Ω/sq, no greater thanabout 300 Ω/sq, no greater than about 200 Ω/sq, no greater than about100 Ω/sq, no greater than about 75 Ω/sq, no greater than about 50 Ω/sq,no greater than about 25 Ω/sq, no greater than about 20 Ω/sq, no greaterthan about 15 Ω/sq, no greater than about 10 Ω/sq, and down to about 1Ω/sq or less. At a transmittance of about 90% or greater, a sheetresistance can be no greater than about 500 Ω/sq, no greater than about400 Ω/sq, no greater than about 350 Ω/sq, no greater than about 300Ω/sq, no greater than about 200 Ω/sq, no greater than about 100 Ω/sq, nogreater than about 75 Ω/sq, no greater than about 50 Ω/sq, no greaterthan about 25 Ω/sq, no greater than about 20 Ω/sq, no greater than about15 Ω/sq, no greater than about 10 Ω/sq, and down to about 1 Ω/sq orabout 0.1 Ω/sq, or less.

Incorporation of Additives into Ceramics

Certain embodiments of transparent conductors include ceramics thatincorporate additives, such as by surface embedding the ceramics withnanowires, nanotubes, or both. Some industries, such as the solarindustry, specify that transparent conductors should withstandprocessing temperatures as high as about 600° C. In the case of silvernanowires, for example, exposing the silver nanowires to hightemperatures can cause their decomposition into silver nanoparticles,disintegration, degradation, or other detrimental effect, therebypotentially losing an electrical percolation network. Advantageously,embedding or incorporating silver nanowires or other types ofelectrically conductive or semiconducting additives into ceramics canprotect the additives from decomposition, thereby maintaining desiredlevels of electrical conductivity even when exposed to hightemperatures. In some embodiments, transparent conductors can be exposedto temperatures up to (or at least) about 600° C., up to (or at least)about 550° C., up to (or at least) about 500° C., up to (or at least)about 450° C., or up to (or at least) about 400° C., with substantiallyno decrease, no greater than about 3% decrease, no greater than about 5%decrease, no greater than about 10% decrease, no greater than about 15%decrease, no greater than about 20% decrease, no greater than about 30%decrease, no greater than about 40% decrease, or no greater than about50% decrease in observed transmittance, and with substantially noincrease, no greater than about 100% increase, no greater than about 50%increase, no greater than about 40% increase, no greater than about 30%increase, no greater than about 20% increase, no greater than about 15%increase, no greater than about 10% increase, no greater than about 5%increase, or no greater than about 3% increase in observed resistance(e.g., sheet resistance).

FIG. 1A and FIG. 1B illustrate examples of transparent conductors 120and 126 implemented in accordance with embodiments of the invention.Specifically, FIG. 1A is a schematic of surface-embedded additives 130that form a network that is partially exposed and partially buried intoa top, embedding surface 134 of a host material 132, which correspondsto a ceramic in the form of a substrate. The embedding surface 134 alsocan be a bottom surface of the host material 132. As illustrated in FIG.1A, the network of the additives 130 is localized adjacent to theembedding surface 134 and within an embedded region 138 of the hostmaterial 132, with a remainder of the host material 132 largely devoidof the additives 130. In the illustrated embodiment, the embedded region138 is relatively thin (e.g., having a thickness less than or much lessthan an overall thickness of the host material 132, or having athickness comparable to a characteristic dimension of the additives130), and, therefore, can be referred to as “planar” or “planar-like.”Through embedding into the host material 132, the additives 130 areprotected from decomposition when exposed to high temperatures, therebymaintaining desired levels of electrical conductivity.

FIG. 1B is a schematic of surface-embedded additives 154 that form anetwork that is partially exposed and partially buried into a top,embedding surface 156 of a host material 158, which corresponds to aceramic in the form of a coating or other secondary material that isdisposed on top of a substrate 160. As illustrated in FIG. 1B, thenetwork of the additives 154 can be localized adjacent to the embeddingsurface 156 and within an embedded region 162 of the host material 158,with a remainder of the host material 158 largely devoid of theadditives 154. It is also contemplated that the additives 154 can bedistributed throughout a larger volume fraction within the host material158, such as in the case of a relatively thin coating having a thicknesscomparable to a characteristic dimension of the additives 154. In theillustrated embodiment, the embedded region 162 is relatively thin, and,therefore, can be referred to as “planar” or “planar-like.” Through atleast partial embedding into the host material 158, the additives 154are protected from decomposition when exposed to high temperatures,thereby maintaining desired levels of electrical conductivity.

In some embodiments, additives can be exposed at the surface, while, inother embodiments, the additives can be completely beneath the surface(e.g., an embedded region is entirely below the embedding surface). Insome cases, when the additives are completely beneath the surface, atransparent conductor can still exhibit surface conductivity due to aceramic layer being thin enough to allow tunneling, beingsemiconducting, being conducting, or a combination thereof.

The transparent conductors 120 and 126 as well as certain othertransparent conductors described herein can be formed according tomanufacturing methods that can be carried out in a highly-scalable,rapid, and low-cost fashion, in which additives are durably incorporatedinto a wide variety of host materials. Some embodiments of themanufacturing methods can be generally classified into two categories:(1) surface-embedding additives into a dry composition to yield a hostmaterial with the surface-embedded additives; and (2) surface-embeddingadditives into a wet composition to yield a host material with thesurface-embedded additives. It will be understood that suchclassification is for ease of presentation, and that “dry” and “wet” canbe viewed as relative terms (e.g., with varying degrees of dryness orwetness), and that the manufacturing methods can apply to a continuumspanned between fully “dry” and fully “wet.” Accordingly, processingconditions and materials described with respect to one category (e.g.,dry composition) can also apply with respect to another category (e.g.,wet composition), and vice versa. It will also be understood thathybrids or combinations of the two categories are contemplated, such aswhere a wet composition is dried or otherwise converted into a drycomposition, followed by surface-embedding of additives into the drycomposition to yield a host material with the surface-embeddedadditives. It will further be understood that, although “dry” and “wet”sometimes may refer to a level of water content or a level of solventcontent, “dry” and “wet” also may refer to another characteristic of acomposition in other instances, such as a degree of cross-linking orpolymerization.

Attention first turns to FIG. 2A and FIG. 2B, which illustrate examplesof manufacturing methods for surface-embedding additives into drycompositions, according to embodiments of the invention.

By way of overview, the illustrated embodiments involve the applicationof an embedding fluid to allow additives to be embedded into a drycomposition, such as one including a ceramic, a ceramic precursor, or acombination thereof. In general, the embedding fluid serves toreversibly alter the state of the dry composition, such as bydissolving, reacting, softening, solvating, swelling, or any combinationthereof, thereby facilitating embedding of the additives into the drycomposition. For example, the dry composition can include a ceramic or aceramic precursor in the form of a gel or a semisolid, and applicationof the embedding fluid can cause the gel to be swollen by filling poreswith the fluid, by elongation of partially uncondensed oligomeric orpolymeric chains, or both. As a further example, the dry composition caninclude a ceramic or a ceramic precursor in the form of an ionicpolymer, such as sodium silicate or another alkali metal silicate, andapplication of the embedding fluid can dissolve at least a portion ofthe ionic polymer to allow embedding of the additives. The embedding ofthe additives is then followed by hardening or other change in state ofthe softened or swelled composition, resulting in a host material havingthe additives embedded therein. For example, the softened or swelledcomposition can be hardened by exposure to ambient conditions, or bycooling the softened or swelled composition. In other embodiments, thesoftened or swelled composition is hardened by evaporating or otherwiseremoving at least a portion of the embedding fluid (or other liquid orliquid phase that is present), applying airflow, applying a vacuum, orany combination thereof. In the case of a ceramic precursor, curing canbe carried out after embedding such that the ceramic precursor isconverted into a glass or another ceramic. Curing can be omitted,depending on the particular application. Depending on the particularceramic precursor (e.g., a silane), more or less heat can be involved toachieve various degrees of curing or conversion into a fully reacted orfully formed glass.

Referring to FIG. 2A, a dry composition 200 can be provided in the formof a sheet, a film, or other suitable form. The dry composition 200 cancorrespond to a host material and, in particular, can include anymaterial previously listed as suitable host materials, such as aceramic. It is also contemplated that the dry composition 200 cancorrespond to a host material precursor, which can be converted into thehost material by suitable processing, such as drying, curing,cross-linking, polymerizing, or any combination thereof. In someembodiments, the dry composition 200 can include a material with a solidphase as well as a liquid phase, or can include a material that is atleast partially solid or has properties resembling those of a solid,such as a semisolid, a gel, and the like. Next, and referring to FIG.2A, additives 202 and an embedding fluid 204 are applied to the drycomposition 200. The additives 202 can be in solution or otherwisedispersed in the embedding fluid 204, and can be simultaneously appliedto the dry composition 200 via one-step embedding. Alternatively, theadditives 202 can be separately applied to the dry composition 200before, during, or after the embedding fluid 204 treats the drycomposition 200. The separate application of the additives 202 can bereferred as two-step embedding. Subsequently, the resulting hostmaterial 206 has at least some of the additives 502 partially or fullyembedded into a surface of the host material 206. Optionally, suitableprocessing can be carried out to convert the softened or swelledcomposition 200 into the host material 206. During device assembly, thehost material 206 with the embedded additives 202 can be laminated orotherwise connected to adjacent device layers, or can serve as asubstrate onto which adjacent device layers are formed, laminated, orotherwise applied.

FIG. 2B is a process flow similar to FIG. 2A, but with a dry composition208 provided in the form of a coating that is disposed on top of asubstrate 210. The dry composition 208 can correspond to a hostmaterial, or can correspond to a host material precursor, which can beconverted into the host material by suitable processing, such as drying,curing, cross-linking, polymerizing, or any combination thereof. Othercharacteristics of the dry composition 208 can be similar to thosedescribed above with reference to FIG. 2A, and are not repeated below.Referring to FIG. 2B, the substrate 210 can be transparent or opaque,can be flexible or rigid, and can be comprised of, for example, apolymer, an ionomer, a coated polymer (e.g., a PET film with a PMMAhardcoat), ethylene vinyl acetate (or EVA), cyclic olefin polymer (orCOP), cyclic olefin copolymer (or COC), polyvinyl butyral (or PVB),thermoplastic olefin (or TPO), thermoplastic polyurethane (or TPU),polyethylene (or PE), polyethylene terephthalate (or PET), polyethyleneterephthalate glycol (or PETG), polycarbonate, polyvinyl chloride (orPVC), polypropylene (or PP), acrylic-based polymer, acrylonitrilebutadiene styrene (or ABS), ceramic, glass, silicon, metal (e.g.,stainless steel or aluminum), or any combination thereof, as well as anyother material previously listed as suitable host materials. Thesubstrate 210 can serve as a temporary substrate that is subsequentlyremoved during device assembly, or can be retained in a resulting deviceas a layer or other component of the device. Next, additives 212 and anembedding fluid 214 are applied to the dry composition 208. Theadditives 212 can be in solution or otherwise dispersed in the embeddingfluid 214, and can be simultaneously applied to the dry composition 208via one-step embedding. Alternatively, the additives 212 can beseparately applied to the dry composition 208 before, during, or afterthe embedding fluid 214 treats the dry composition 208. As noted above,the separate application of the additives 212 can be referred astwo-step embedding. Subsequently, the resulting host material 216 (whichis disposed on top of the substrate 210) has at least some of theadditives 212 partially or fully embedded into a surface of the hostmaterial 216. Optionally, suitable processing can be carried out toconvert the softened or swelled composition 208 into the host material216. During device assembly, the host material 216 with the embeddedadditives 212 can be laminated or otherwise connected to adjacent devicelayers, or can serve as a substrate onto which adjacent device layersare formed, laminated, or otherwise applied.

In some embodiments, additives are dispersed in an embedding fluid, ordispersed in a separate carrier fluid and separately applied to a drycomposition. Dispersion can be accomplished by mixing, milling,sonicating, shaking (e.g., wrist action shaking, rotary shaking),vortexing, vibrating, flowing, chemically modifying the additives'surfaces, chemically modifying a fluid, increasing the viscocity of thefluid, adding a dispersing or suspending agent to the fluid, adding astabilization agent to the fluid, changing the polarity of the fluid,changing the hydrogen bonding of the fluid, changing the pH of thefluid, or otherwise processing the additives to achieve the desireddispersion. The dispersion can be uniform or non-uniform, and can bestable or unstable. A carrier fluid can serve as an embedding fluid(e.g., an additional embedding fluid), or can have similarcharacteristics as an embedding fluid. In other embodiments, a carrierfluid can serve as a transport medium to carry or convey additives, butis otherwise substantially inert towards the additives and the drycomposition.

Fluids (e.g., embedding fluids and carrier fluids) can include liquids,gases, or supercritical fluids. Combinations of different types offluids are also suitable. Fluids can include one or more solvents. Forexample, a fluid can include water, an ionic or ion-containing solution,an ionic liquid, an organic solvent (e.g., a polar, organic solvent; anon-polar, organic solvent; an aprotic solvent; a protic solvent; apolar aprotic solvent, or a polar, protic solvent); an inorganicsolvent, or any combination thereof. Oils also can be consideredsuitable fluids. Salts, surfactants, dispersants, stabilizers, polymers,monomers, oligomers, cross-linking agents, polymerization agents, acids,bases, or binders can also be included in the fluids.

Examples of suitable organic solvents include 2-methyltetrahydrofuran, achloro-hydrocarbon, a fluoro-hydrocarbon, a ketone, a paraffin,acetaldehyde, acetic acid, acetic anhydride, acetone, acetonitrile, analkyne, an olefin, aniline, benzene, benzonitrile, benzyl alcohol,benzyl ether, butanol, butanone, butyl acetate, butyl ether, butylformate, butyraldehyde, butyric acid, butyronitrile, carbon disulfide,carbon tetrachloride, chlorobenzene, chlorobutane, chloroform,cycloaliphatic hydrocarbons, cyclohexane, cyclohexanol, cyclohexanone,cyclopentanone, cyclopentyl methyl ether, diacetone alcohol,dichloroethane, dichloromethane, diethyl carbonate, diethyl ether,diethylene glycol, diglyme, di-isopropylamine, dimethoxyethane, dimethylformamide, dimethyl sulfoxide, dimethylamine, dimethylbutane,dimethylether, dimethylformamide, dimethylpentane, dimethylsulfoxide,dioxane, dodecafluoro-1-hepatanol, ethanol, ethyl acetate, ethyl ether,ethyl formate, ethyl propionate, ethylene dichloride, ethylene glycol,formamide, formic acid, glycerine, heptane, hexafluoroisopropanol (orHFIP), hexamethylphosphoramide, hexamethyl phosphorous triamide, hexane,hexanone, hydrogen peroxide, hypochlorite, i-butyl acetate, i-butylalcohol, i-butyl formate, i-butylamine, i-octane, i-propyl acetate,i-propyl ether, isopropanol, isopropylamine, ketone peroxide, methanoland calcium chloride solution, methanol, methoxyethanol, methyl acetate,methyl ethyl ketone (or MEK), methyl formate, methyl n-butyrate, methyln-propyl ketone, methyl t-butyl ether, methylene chloride, methylene,methylhexane, methylpentane, mineral oil, m-xylene, n-butanol, n-decane,n-hexane, nitrobenzene, nitroethane, nitromethane, nitropropane,2-N-methyl-2-pyrrolidinone, n-propanol, octafluoro-1-pentanol, octane,pentane, pentanone, petroleum ether, phenol, propanol, propionaldehyde,propionic acid, propionitrile, propyl acetate, propyl ether, propylformate, propylamine, propylene glycol, p-xylene, pyridine, pyrrolidine,t-butanol, t-butyl alcohol, t-butyl methyl ether, tetrachloroethane,tetrafluoropropanol (or TFP), tetrahydrofuran (or THF),tetrahydronaphthalene, toluene, triethyl amine, trifluoroacetic acid,trifluoroethanol (or TFE), trifluoropropanol, trimethylbutane,trimethylhexane, trimethylpentane, valeronitrile, xylene, xylenol, orany combination thereof. Alcohols including from one to ten carbon atoms(i.e., C₁-C₁₀ alcohols, such as C₁-C₆ alcohols) can be consideredsuitable, such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol,2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol,2-pentanol, 3-pentanol, 2-2-dimethyl-1-propanol, 1-hexanol, as well ascombinations, functionalized forms, and mixtures thereof with anotherfluid such as water. Alcohols include primary alcohols (e.g., n-propylalcohol, isobutyl alcohol), secondary alcohols (e.g., isopropyl alcohol,cyclohexanol), tertiary alcohols (e.g., tert-amyl alcohol), or anycombination thereof. Other examples of suitable alcohols includemonohydric alcohols (e.g., methanol, ethanol, isopropyl alcohol, butylalcohol, butanol, pentanol, hexadecan-1-ol, amyl alcohol, cetylalcohol), polyhydric alcohols (e.g., ethylene glycol, glycerin,Butan-1,2,3,4-tetraol, erythritol, Pentane-1,2,3,4,5-pentol, xylitol,Hexane-1,2,3,4,5,6-hexyl, mannitol, sorbitol,Heptane-1,2,3,4,5,6,7-heptol, volemitol), unsaturated aliphatic alcohols(e.g., Prop-2-ene-1-ol, allyl alcohol, 3,7-Dimethyloca-2,6-dien-1-ol,Geraniol, prop-2-in-1-ol, propargyl alcohol), alicyclic alcohols (e.g.,cyclohexane-1,2,3,4,5,6-hexyl, inositol,2-(2-propyl)-5-methyl-cyclohexane-1-ol, Menthol), as well ascombinations, functionalized forms, and mixtures thereof with otherfluids (e.g., water).

Suitable inorganic solvents include, for example, water, ammonia, sodiumhydroxide, sulfur dioxide, sulfuryl chloride, sulfuryl chloridefluoride, phosphoryl chloride, phosphorus tribromide, dinitrogentetroxide, antimony trichloride, bromine pentafluoride, hydrogenfluoride, or any combination thereof.

Suitable ionic solutions include, for example, choline chloride, urea,malonic acid, phenol, glycerol, 1-alkyl-3-methylimidazolium,1-alkylpyridinium, N-methyl-N-alkylpyrrolidinium,1-butyl-3-methylimidazolium hexafluorophosphate, ammonium, choline,imidazolium, phosphonium, pyrazolium, pyridinium, pyrrolidnium,sulfonium, 1-ethyl-1-methylpiperidinium methyl carbonate,4-ethyl-4-methylmorpholinium methyl carbonate, or any combinationthereof. Other methylimidazolium solutions can be considered suitable,including 1-ethyl-3-methylimidazolium acetate,1-butyl-3-methylimidazolium tetrafluoroborate,1-n-butyl-3-methylimidazolium tetrafluoroborate,1-butyl-3-methylimidazolium hexafluorophosphate,1-n-butyl-3-methylimidazoliumhexafluoro phosphate,1-butyl-3-methylimidazolium 1,1,1-trifluoro-N[(trifluoromethyl)sulfonyl]methanesulfonamide,1-butyl-3-methylimidazolium bis(trifluoro methylsulfonyl)imide,1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl] amide, and1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide, or anycombination thereof.

Other suitable fluids include halogenated compounds, imides, and amides,such as N-ethyl-N,N-bis(1-methylethyl)-1-heptanaminiumbis[(trifluoromethyl)sulfonyl]imide, ethylheptyl-di-(1-methylethyl)ammonium1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methane sulfonamide,ethylheptyl-di-(1-methyl ethyl)ammonium bis(trifluoromethylsulfonyl)imide, ethylheptyl-di-(1-methylethyl)ammoniumbis[(trifluoromethyl)sulfonyl]amide, or any combination thereof. A fluidcan also include ethylheptyl-di-(1-methylethyl)ammoniumbis[(trifluoromethyl)sulfonyl]imide, N₅N₅N-tributyl-1-octanaminiumtrifluoromethane sulfonate, tributyloctylammonium triflate,tributyloctylammonium trifluoromethanesulfonate,N,N,N-tributyl-1-hexanaminium bis[(trifluoromethyl)sulfonyl]imide,tributylhexylammonium1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide,tributylhexylammonium bis(trifluoromethylsulfonyl)imide,tributylhexylammonium bis[(trifluoromethyl)sulfonyl]amide,tributylhexylammonium bis[(trifluoromethyl)sulfonyl] imide,N,N,N-tributyl-1-heptanaminium bis[(trifluoromethyl)sulfonyl]imide,tributylheptylammonium 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide, tributylheptylammoniumbis(trifluoromethylsulfonyl) imide; tributylheptylammoniumbis[(trifluoromethyl)sulfonyl]amide, tributylheptylammoniumbis[(trifluoromethyl)sulfonyl]imide, N,N,N-tributyl-1-octanaminiumbis[(trifluoromethyl) sulfonyl]imide, tributyloctylammonium1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methane sulfonamide,tributyloctylammonium bis(trifluoromethylsulfonyl)imide,tributyloctylammonium bis[(trifluoromethyl)sulfonyl]amide,tributyloctylammonium bis[(trifluoromethyl)sulfonyl]imide,1-butyl-3-methylimidazolium trifluoroacetate,1-methyl-1-propylpyrrolidinium1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide,1-methyl-1-propylpyrrolidinium bis(trifluoro methylsulfonyl)imide,1-methyl-1-propylpyrrolidinium bis[(trifluoromethyl)sulfonyl] amide,1-methyl-1-propylpyrrolidinium bis[(trifluoromethyl)sulfonyl] imide,1-butyl-1-methylpyrrolidinium1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide,1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide,1-butyl-1-methylpyrrolidinium bis [(trifluoromethyl)sulfonyl]amide,1-butyl-1-methylpyrrolidinium bis[(trifluoromethyl)sulfonyl]imide,1-butylpyridinium1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide,1-butylpyridinium bis(trifluoromethylsulfonyl)imide, 1-butylpyridiniumbis[(trifluoromethyl) sulfonyl] amide, 1-butylpyridiniumbis[(trifluoromethyl)sulfonyl]imide, 1-butyl-3-methyl imidazoliumbis(perfluoroethylsulfonyl)imide, butyltrimethylammoniumbis(trifluoromethyl sulfonyl)imide, 1-octyl-3-methylimidazolium1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide,1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide,1-octyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]amide,1-octyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide,1-ethyl-3-methylimidazolium tetrafluoroborate,N₅N₅N-trimethyl-1-hexanaminium bis[(trifluoromethyl)sulfonyl]imide,hexyltrimethylammonium1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide,hexyltrimethylammonium bis(trifluoromethylsulfonyl)imide,hexyltrimethylammonium bis[(trifluoromethyl)sulfonyl] amide,hexyltrimethylammonium bis[(trifluoromethyl)sulfonyl] imide,N,N,N-trimethyl-1-heptanaminium bis[(trifluoromethyl)sulfonyl]imide,heptyltrimethylammonium1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide,heptyltrimethylammonium bis(trifluoro methylsulfonyl)imide,heptyltrimethylammonium bis[(trifluoromethyl)sulfonyl]amide,heptyltrimethylammonium bis[(trifluoromethyl)sulfonyl]imide,N,N,N-trimethyl-1-octanaminium bis[(trifluoromethyl)sulfonyl]imide,trimethyloctylammonium 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide, trimethyloctylammoniumbis(trifluoromethylsulfonyl) imide, trimethyloctylammoniumbis[(trifluoromethyl)sulfonyl]amide, trimethyloctylammoniumbis[(trifluoromethyl)sulfonyl]imide, 1-ethyl-3-methylimidazolium ethylsulfate, or any combination thereof.

Control over surface-embedding of additives can be achieved through theproper balancing of the swelling-dispersion-evaporation-applicationstages. This balance can be controlled by, for example, a solvent-hostmaterial interaction parameter, sizes of additives, reactivity andvolatility of an embedding fluid, impinging additive momentum orvelocity, temperature, humidity, pressure, and others factors. Moreparticularly, relevant processing parameters for surface-embedding arelisted below for some embodiments of the invention:

Embedding Fluid Selection:

-   -   Compatibility of embedding fluid with surface (e.g., matching or        comparison of Hildebrand and Hansen solubility parameters,        dielectric constant, partition coefficient, pKa, etc.)    -   Evaporation rate, boiling point, vapor pressure, enthalpy of        vaporization of embedding fluid    -   Diffusion of embedding fluid into surface: thermodynamic and        kinetics considerations    -   Viscosity of embedding fluid    -   Surface tension of embedding fluid, wicking, and capillary        effects    -   Azeotroping, miscibility, and other interactions with other        fluids    -   Capillary forces    -   Stability of additives in the fluid compared to stability of the        additives in the host material

Application Conditions:

-   -   Duration of fluid-surface exposure    -   Temperature    -   Humidity    -   Application method (e.g., spraying, printing, rolling coating,        gravure coating, slot-die coating, capillary coating, meniscus        coating, cup coating, blade coating, airbrushing, immersion, dip        coating, etc.)    -   Impact/momentum/velocity of additives onto surface (e.g., may        influence depth or extent of embedding)    -   Shear applied to solvent between host material and applicator    -   Post-processing conditions (e.g., heating, evaporation, fluid        removal, air-drying, etc.)

Host Material:

-   -   Surface energy    -   Roughness, porosity, and surface area    -   Pre-treatments (e.g., ultraviolet ozonation, base etch,        cleaning, solvent priming, heating, curing, vacuum, etc.)    -   Degree of crosslinking, polymerization, and/or gellation    -   Molecular weight    -   Crystallinity    -   Dispersion/suspension of additives in fluid prior to embedding        (e.g., additives can remain dispersed in solution through        physical agitation, chemical/capping stabilization, steric        stabilization, or are inherently solubilized)    -   Mitigation of undesired effects (e.g., hazing, crazing,        blushing, irreversible destruction of host material, uneven        wetting, roughness, etc.)

Some, or all, of the aforementioned parameters can be altered orselected to tune a depth or an extent of embedding of additives into agiven host material. For example, higher degrees of embedding deep intoa surface of a host material can be achieved by increasing a solvencypower of an embedding fluid interacting with the host material, matchingclosely Hansen solubility parameters of the embedding fluid-substrate,prolonging the exposure duration of the embedding fluid in contact withthe host material, increasing an amount of the embedding fluid incontact with the host material, elevating a temperature of the system,increasing a momentum of additives impinging onto the host material,increasing a diffusion of either, or both, of the embedding fluid andthe additives into the host material, or any combination thereof.

Fluids (e.g., embedding fluids and carrier fluids) can also includesalts, surfactants, stabilizers, and other agents useful in conferring aparticular set of characteristics on the fluids. Stabilizers can beincluded based on their ability to at least partially inhibitinter-additive agglomeration. Other stabilizers can be chosen based ontheir ability to preserve the functionality of additives. Butylatedhydroxytoluene (or BHT), for instance, can act as a good stabilizer andas an antioxidant. Other agents can be used to adjust rheologicalproperties, evaporation rate, and other characteristics.

Fluids and additives can be applied so as to be largely stationaryrelative to a surface of a dry composition. In other embodiments,application is carried out with relative movement, such as by spraying afluid onto a surface, by conveying a dry composition through a fallingcurtain of a fluid, or by conveying a dry composition through a pool orbath of a fluid. Application of fluids and additives can be effected byairbrushing, atomizing, nebulizing, spraying, electrostatic spraying,pouring, rolling, curtaining, wiping, spin casting, dripping, dipping,painting, flowing, brushing, immersing, patterning (e.g., stamping,inkjet printing, controlled spraying, controlled ultrasonic spraying,and so forth), flow coating methods (e.g., slot die, capillary coating,meyer rod, blade coating, cup coating, draw down, and the like),printing, gravure printing, lithography, screen printing, flexoprinting, offset printing, roll coating, inkjet printing, intaglioprinting, or any combination thereof. In some embodiments, additives arepropelled, such as by a sprayer, onto a surface, thereby facilitatingembedding by impact with the surface. In other embodiments, a gradientis applied to a fluid, additives, or both. Suitable gradients includemagnetic and electric fields. The gradient can be used to apply,disperse, or propel the fluid, additives, or both, onto a surface. Insome embodiments, the gradient is used to manipulate additives so as tocontrol the extent of embedding. An applied gradient can be constant orvariable. Gradients can be applied before a dry composition is softenedor swelled, while the dry composition remains softened or swelled, orafter the dry composition is softened or swelled. It is contemplatedthat a dry composition can be heated to achieve softening, and thateither, or both, a fluid and additives can be heated to promoteembedding. In some embodiments, embedding of additives can be achievedprimarily or solely through application of an embedding fluid, withoutrequiring application of gradients or external pressure. In someembodiments, embedding of additives can be achieved through applicationof pressure (e.g., pressure rollers) in place of, or in conjunctionwith, an embedding fluid.

Application of fluids and additives and embedding of the additives canbe spatially controlled to yield patterns. In some embodiments, spatialcontrol can be achieved with a physical mask, which can be placedbetween an applicator and a surface to block a segment of appliedadditives from contacting the surface, resulting in controlledpatterning of additive embedding. In other embodiments, spatial controlcan be achieved with a photomask. A positive or negative photomask canbe placed between a light source and a surface, which can correspond toa photoresist. Light transmitted through non-opaque parts of thephotomask can selectively affect a solubility of exposed parts of thephotoresist, and resulting spatially controlled soluble regions of thephotoresist can permit controlled embedding of additives. In otherembodiments, spatial control can be achieved through the use of electricgradients, magnetic gradients, electromagnetic fields, thermalgradients, pressure or mechanical gradients, surface energy gradients(e.g., liquid-solid-gas interfaces, adhesion-cohesion forces, andcapillary effects), or any combination thereof. Spatial control can alsobe achieved by printing a material that differs from a host material andin which embedding does not occur (or is otherwise inhibited).

As noted above, additives can be dispersed in an embedding fluid, andapplied to a dry composition along with the embedding fluid via one-stepembedding. Additives also can be applied to a dry composition separatelyfrom an embedding fluid via two-step embedding. In the latter scenario,the additives can be applied in a wet form, such as by dispersing in acarrier fluid or by dispersing in the same embedding fluid or adifferent embedding fluid. Still in the latter scenario, the additivescan be applied in a dry form, such as in the form of aerosolized powder.It is also contemplated that the additives can be applied in a quasi-dryform, such as by dispersing the additives in a carrier fluid that isvolatile, such as methanol, another low boiling point alcohol, oranother low boiling point organic solvent, which substantially vaporizesprior to impact with a dry composition.

By way of example, one embodiment involves spraying, airbrushing, orotherwise atomizing a solution of nanowires or other additives dispersedin an appropriate carrier fluid onto a dry composition.

As another example, one embodiment involves pre-treating a drycomposition by spraying or otherwise contacting an embedding fluid withthe dry composition, and then, after the passage of time t₁, spraying orairbrushing nanowires or other additives with velocity such that thecombination of the temporarily softened dry composition and the velocityof the impinging nanowires allow rapid and durable surface-embedding ofthe nanowires. t₁ can be, for example, in the range of about 0nanosecond to about 24 hours, such as from about 1 nanosecond to about24 hours, from about 1 nanosecond to about 1 hour or from about 1 secondto about 1 hour. Two spray nozzles can be simultaneously or sequentiallyactivated, with one nozzle dispensing the embedding fluid, and the othernozzle dispensing, with velocity, atomized nanowires dispersed in acarrier fluid towards the dry composition. Air-curing or highertemperature annealing optionally can be included.

As another example, one embodiment involves spraying, airbrushing, orotherwise atomizing a solution of nanowires or other additives dispersedin a carrier fluid onto a dry composition. After the passage of time t₂,a second spraying, airbrushing, or atomizing operation is used to applyan embedding fluid so as to permit efficient surface-embedding of thenanowires. t₂ can be, for example, in the range of about 0 nanosecond toabout 24 hours, such as from about 1 nanosecond to about 24 hours, fromabout 1 nanosecond to about 1 hour or from about 1 second to about 1hour. Two spray nozzles can be simultaneously or sequentially activated,with one nozzle dispensing the embedding fluid, and the other nozzledispensing, with velocity, atomized nanowires dispersed in the carrierfluid towards the dry composition. Air-curing or higher temperatureannealing optionally can be included.

As a further example, one embodiment involves applying nanowires orother additives onto a dry composition composed of sodium silicate oranother alkali metal silicate or other solid glass. Eithersimultaneously or as a separate operation, an embedding fluid composedof heated, basic water is applied in liquid or vapor form to the sodiumsilicate at either room temperature or elevated temperature, whichcauses the sodium silicate to at least partially dissolve, therebypermitting entry of the nanowires into the dissolved sodium silicate.The water is evaporated or otherwise removed, causing the sodiumsilicate to re-solidify with the nanowires embedded within the sodiumsilicate. Air-curing or higher temperature annealing optionally can beincluded.

A time period for exposure or otherwise contacting an embedding fluidwith a dry composition can be selected, for example, according to adesired extent of embedding, while mitigating against undesired effectssuch as hazing, crazing, blushing, and so forth. In some embodiments, aexposure time can be, for example, in the range of about 0.1 second toabout 24 hours, such as from about 0.5 second to about 12 hours, fromabout 1 second to about 6 hours, from about 1 second to about 3 hours,from about 1 second to about 2 hours, from about 1 second to about 1hour, from about 1 minute to about 50 minutes, from about 1 minute toabout 40 minutes, from about 1 minute to about 30 minutes, or from about1 minute to about 20 minutes.

As discussed above, embedding silver nanowires or other types ofelectrically conductive or semiconducting additives into ceramics canprotect the additives from decomposition when exposed to hightemperatures. In some embodiments, control over an extent of embeddingof the additives is desirable to allow a balance to be attained between“over-embedding” and “under-embedding” the additives.

Referring to an “under-embedding” scenario illustrated in FIG. 3A, ifnanowires 300 are embedded too shallow into a host material 302, theresulting nanowires 300 are exposed for electrical contact but aresusceptible to abrasion, resulting in a nanowire network that isunstable and having non-uniform conductivity. Referring to an“over-embedding” scenario illustrated in FIG. 3B, if the nanowires 300are embedded deeply into the host material 302, the resulting nanowires300 are substantially or largely covered by the host material 302. Thiscoverage can protect the nanowires 300 against abrasion or against othertypes of degradation (e.g., oxidation, sulfidation), but, if thethickness of the coverage of the host material 302 is too thick (and thehost material is non-conductive), it can impede electrical contact at asurface of the host material 302. Moreover, this coverage of thenanowires 300 by the host material 302 can result in the host material302 surrounding each nanowire; this can impede the formation ofnanowire-nanowire junctions, and, if the host material 302 thicknessaround each nanowire is too high, it can, thereby, impede the flow of anelectrical current through the nanowires 300.

In terms of attaining a suitable balance between “over-embedding” and“under-embedding” of nanowires or other types of electrically conductiveor semiconducting additives, the additives can be partially embeddedinto a host material to a degree sufficient to resist removal byabrasion while still providing or maintaining a desired level ofelectrical conductivity in a resulting transparent conductor. Suitabletests and values for abrasion resistance and suitable values forelectrical conductivity (in terms of sheet resistance) are set forthabove in the overview section for transparent conductors. Also, in someembodiments, a suitable balance can be attained by localization of theadditives within a “planar” or “planar-like” embedded region of the hostmaterial. In some embodiments, the planar-like embedded region of thehost material is entirely underneath the surface of the host material,while, in other embodiments, the planar-like embedded region of the hostmaterial is adjacent to the embedding surface, with at least a fractionof the additives exposed at a surface of the host material. For example,an embedded region can have a thickness up to about 10 times (or more) acharacteristic dimension of the additives, such as up to about 9 times,up to about 8 times, up to about 7 times, up to about 6 times, up toabout 5 times, up to about 4 times, up to about 3 times, or up to about2 times the characteristic dimension, and down to about 0.05, about 0.1,about 0.2, about 0.3, about 0.4, or about 0.5 times the characteristicdimension. As another example, a thickness of the embedded region can beno greater than about 80% of an overall thickness of the host material,such as no greater than about 50%, no greater than about 40%, no greaterthan about 30%, no greater than about 20%, no greater than about 10%, orno greater than about 5% of the overall thickness. Additional suitablecharacteristics of the embedded region are set forth above in theoverview section for transparent conductors.

For example, embedding of additives into a dry composition can becarried out by providing a ceramic or a ceramic precursor in the form ofa gel or a semisolid that can be swelled by filling pores with anembedding fluid, by elongation of partially uncondensed oligomeric orpolymeric chains, by dissolving at least a portion of the ceramic or theceramic precursor to allow embedding of the additives followed byre-solidification upon fluid removal, or any combination thereof.Additives can be embedded into a surface of a coating while the coatingis swelled, dissolved, or wetted. The chemistry of the embedding processcan be adjusted, such as by adjusting a degree to which a top portion ofthe coating is swelled, dissolved, or wetted. Alternatively, or inconjunction, in the case of a silane-based sol-gel precursor, poreswithin a gel or a semisolid can be at least partially filled with anembedding fluid, or partially uncondensed oligomeric silane chains canbe elongated by interaction with the embedding fluid. In such a case,the chemistry can be tuned by adjusting a degree to which the pores arefilled with the embedding fluid, or a degree to which silane or otheroligomeric or polymeric chains are elongated

Attention next turns to FIG. 2C, which illustrates a manufacturingmethod for surface embedding additives 222 into a wet composition 218,according to an embodiment of the invention. Referring to FIG. 2C, thewet composition 218 is applied to a substrate 220 in the form of acoating that is disposed on top of the substrate 220. The wetcomposition 218 can correspond to a dissolved form of a host materialand, in particular, can include a dissolved form, a colloidal form, ananoparticle form, a sol-form of any material previously listed assuitable host materials, such as a ceramic, a ceramic precursor, or anycombination thereof. It is also contemplated that the wet composition218 can correspond to a host material precursor, which can be convertedinto the host material by suitable processing, such as drying, curing,cross-linking, polymerizing, sintering, calcining, or any combinationthereof. For example, the wet coating composition 218 can be a coatingthat is not fully cured or set, a cross-linkable coating that is notfully cross-linked, which can be subsequently cured or cross-linkedusing suitable polymerization initiators or cross-linking agents, or acoating of monomers, oligomers, or a combination of monomers andoligomers, which can be subsequently polymerized using suitablepolymerization initiators or cross-linking agents. The wet composition218 also can be patterned, for instance, with printing methods likescreen, reverse offset gravure, flexo, or ink-jet, printing, or anothermethod. In some embodiments, the wet composition 218 can include amaterial with a liquid phase as well as a solid phase, or can include amaterial that is at least partially liquid or has properties resemblingthose of a liquid, such as a sol, a semisolid, a gel, and the like. Thesubstrate 220 can be transparent or opaque, can be flexible or rigid,and can be composed of, for example, a polymer, an ionomer, EVA, PVB,TPO, TPU, PE, PET, PETG, PMMA, polycarbonate, PVC, PP, acrylic-basedpolymer, ABS, ceramic, glass, silicon, metal (e.g., stainless steel oraluminum), or any combination thereof, as well as any other materialpreviously listed as suitable host materials. The substrate 220 canserve as a temporary substrate that is subsequently removed duringdevice assembly, or can be retained in a resulting device as a layer orother component of the device.

Next, according to the option on the left-side of FIG. 2C, the additives222 are applied to the wet composition 218 prior to drying or while itremains in a state that permits embedding of the additives 222 withinthe wet composition 218. In some embodiments, application of theadditives 222 is via a flow coating method (e.g., slot die, capillarycoating, meyer rod, cup coating, draw down, and the like). Although notillustrated on the left-side, it is contemplated that an embedding fluidcan be simultaneously or separately applied to the wet composition 218to facilitate the embedding of the additives 222. In some embodiments,embedding of the additives 222 can be achieved through application ofpressure (e.g., pressure rollers) in place of, or in conjunction with,an embedding fluid. Subsequently, the resulting host material 224 has atleast some of the additives 222 partially or fully embedded into asurface of the host material 224. Suitable processing can be carried outto convert the wet composition 218 into the host material 224. Duringdevice assembly, the host material 224 with the embedded additives 222can be laminated or otherwise connected to adjacent device layers, orcan serve as a substrate onto which adjacent device layers are formed,laminated, or otherwise applied.

Certain aspects regarding the application of the additives 222 and theembedding of the additives 222 in FIG. 2C can be carried out usingsimilar processing conditions and materials as described above for FIG.2A and FIG. 2B, and those aspects need not be repeated below. Thefollowing provides additional details on embodiments related to ceramicsand ceramic precursors.

In some embodiments, additives are embedded into a wet composition inthe form of a coating of a liquid ceramic precursor, which may include asolvent and a set of reactive species. The embedding is carried outbefore the solvent has fully dried and/or after drying but beforecuring, followed by the option of curing or otherwise converting theceramic precursor to a fully condensed or restructured glass. Examplesof ceramic precursor reactive species include spin-on glasses, silanes(e.g., Si(OR)(OR′)(OR″)(R′″), Si(OR)(OR′)(R″)(R′″), andSi(OR)(R′)(R″)(R′″), where R, R′, R″, and R′″ are independently selectedfrom hydrogen atoms, alkyl groups, alkenyl groups, alkynyl groups, andaryl groups), titanium analogues of silanes, cerium analogues ofsilanes, magnesium analogues of silanes, germanium analogues of silanes,indium analogues of silanes, tin analogues of silanes, zinc analogues ofsilanes, aluminium analogues of silanes, any mixed metal analogues ofsilanes, siloxanes (e.g., Si(OR)(OR′)(OR″)(OR′″), where R, R′, R″, andR′″ are independently selected from hydrogen atoms, alkyl groups,alkenyl groups, alkynyl groups, and aryl groups), titanium analogues ofsiloxanes, cerium analogues of siloxanes, magnesium analogues ofsiloxanes, germanium analogues of siloxanes, indium analogues ofsiloxanes, tin analogues of siloxanes, zinc analogues of siloxanes,aluminium analogues of siloxanes, any mixed metal analogues ofsiloxanes, alkali metal silicates (e.g., sodium silicate and potassiumsilicate), or any combination thereof. As more specific examples, aceramic precursor reactive species can be a siloxane such astetramethoxysilane (or TMOS), tetraethoxysilane (or TEOS),tetra(isopropoxy)silane, titanium analogues thereof, cerium analoguesthereof, magnesium analogues thereof, germanium analogues thereof,indium analogues thereof, tin analogues thereof, zinc analogues thereof,aluminium analogues thereof, any mixed metal analogues thereof, or anycombination thereof.

In some embodiments, reactive species are at least partially reacted,prior to embedding of additives. Reaction can be carried out by, forexample, hydrolysis in the presence of an acid and a catalyst andfollowed by condensation, thereby yielding oligomeric or polymericchains. For example, silanes and siloxanes can undergo partialcondensation to yield oligomeric or polymeric chains with Si—O—Silinkages, and at least some side groups corresponding to (OR) or (R).

In some embodiments, a liquid ceramic precursor includes at least twodifferent types of reactive species. The different types of species canreact with each other, as exemplified by two or more of TEOS, TMOS, andtetra(isopropoxy)silane, and can be suitably selected in order tocontrol evaporation rate and pre-cured film morphology. Reactive specieswith larger side groups, such as isopropoxy in the case oftetra(isopropoxy)silane versus methoxy in the case of TMOS, can yieldlarger pore sizes when converted into a gel, which larger pore sizes canfacilitate swelling in the presence of an embedding fluid. Also, uponhydrolysis, larger side groups can be converted into correspondingalcohols with lower volatility, such as isopropyl alcohol in the case oftetra(isopropoxy)silane versus methanol in the case of TMOS, which canslow the rate of drying. In other embodiments, the different types ofspecies are not likely to react, such as sodium silicate andtetra(isopropoxy)silane. This can afford facile curing properties of abulk of a matrix formed by drying the silicate, while retaining someamount of delayed condensation to allow embedding of additives.

In some embodiments, reactive species, either prior to reaction orsubsequent to reaction, can include some amount of Si—C or Si—C—Silinkages, which can impart toughness, porosity, or other desirablecharacteristics, such as to allow trapping of a solvent to slow the rateof drying or to promote swelling in the presence of an embedding fluid.

In some embodiments, reactive species, either prior to reaction orsubsequent to reaction, can include Si—OR groups, where R is a longchain side group with low volatility to slow the rate of drying of acoating of a liquid ceramic precursor. In other embodiments, reactivespecies can include Si—R′ groups, where R′ is a long chain side groupwith low volatility to slow the rate of drying of a coating of a liquidceramic precursor. Either, or both, of R and R′ also can havecharacteristics to interact and retain a solvent, thereby slowing thedrying process. For example, R and R′ can have polarity, non-polarity,aliphatic characteristics, or other characteristics that match those ofthe solvent.

In some embodiments, a solvent included in a liquid ceramic precursorcan include water, an alcohol, dimethylformamide, dimethyl sulfoxide,another polar solvent, another non-polar solvent, any other suitablefluid listed above, or any combination thereof. For example, the solventcan be non-polar, and water can be used heterogeneously duringhydrolysis, with complete condensation occurring after drying a coatingof the ceramic precursor. As another example, a combination of solventscan be selected, such that a major component has high volatility inorder to carry, wet, or level reactive species, whereas a minorcomponent has low volatility to delay drying of the coating. It is alsocontemplated that the reactive species can form a relatively smallfraction of a total coating volume to slow drying.

In some embodiments, a liquid ceramic precursor can be applied to asubstrate using a wide variety of coating methods, such as aroll-to-roll process, roll coating, gravure coating, slot dye coating,knife coating, spray coating, and spin coating. For example, the liquidceramic precursor can be applied by spin coating, and additives can bedeposited upon the start of spin coating or after the start of spincoating, but before the resulting coating has dried on a spinner.

In some embodiments, additives can be dispersed in a carrier fluid, andthen applied in a wet form to a liquid ceramic precursor. The carrierfluid can include the same solvent (or another solvent having similarcharacteristics) as a low volatility component of the liquid ceramicprecursor in order to reduce or avoid adverse interaction upon impact.It is also contemplated that the carrier fluid can be volatile (e.g.,methanol or another low boiling alcohol), which substantially evaporates(or at least partially evaporates) prior to impact. Another example of asuitable carrier fluid is water.

In some embodiments, curing can be carried out after embedding such thata liquid ceramic precursor is converted into a glass. For example,curing can involve heating to a temperature in the range of about 400°C. to about 500° C. in nitrogen (optionally containing water vapor(possibly saturated)), heating up to a temperature sufficient to removeresidual solvent (e.g., from about 100° C. to about 150° C.), or heatingto a temperature in the range of about 800° C. to about 900° C. to forma fully condensed glass. Curing can be omitted, such as in the case ofsodium silicate (or another alkali silicate) that can dry under ambientconditions into a robust “clear coat.” In some embodiments, curing canalso serve as a sintering/annealing operation for embedded nanowires orother additives, for instance, heating up to a temperature for alow-temperature sintering/fusing of nanowire junctions (e.g., from about100° C. to about 250° C.). In some embodiments, pre-curing can becarried out before embedding in order to stabilize a coating towithstand shear or fluid forces, but still be in a state to allowembedding of additives.

Turning back to FIG. 2C and referring to the option on the right-side,the wet composition 218 can be initially converted into a drycomposition 226 by suitable processing, such as by at least partiallydrying, curing, cross-linking, polymerization, or any combinationthereof. Next, the additives 222 and an embedding fluid 228 can beapplied to the dry composition 226. The additives 222 can be in solutionor otherwise dispersed in the embedding fluid 228, and can besimultaneously applied to the dry composition 226 via one-stepembedding. Alternatively, the additives 222 can be separately applied tothe dry composition 226 before, during, or after the embedding fluid 228treats the dry composition 226. As noted above, the separate applicationof the additives 222 can be referred as two-step embedding.Subsequently, the resulting host material 224 has at least some of theadditives 222 partially or fully embedded into the surface of the hostmaterial 224. Optionally, suitable processing can be carried out toconvert the dry composition 226 into the host material 224, such as byadditional drying, curing, cross-linking, polymerization, or anycombination thereof. Any, or all, of the manufacturing stagesillustrated in FIG. 2C can be carried out in the presence of a vaporenvironment of a suitable fluid (e.g., an embedding fluid or othersuitable fluid) to facilitate the embedding of the additives 222, toslow drying of the wet composition 218, or both.

Certain aspects regarding the application of the additives 222 and theembedding fluid 228 and the embedding of the additives 222 in FIG. 2Ccan be carried out using similar processing conditions and materials asdescribed above for FIG. 2A and FIG. 2B, and those aspects need not berepeated below. In particular, and in at least certain aspects, theprocessing conditions for embedding the additives 222 into the drycomposition 226 of FIG. 2C can be viewed as largely parallel to thoseused when embedding the additives 212 into the dry composition 208 ofFIG. 2B. The following provides further details on embodiments relatedto ceramics and ceramic precursors.

In some embodiments, additives are embedded into a dry composition inthe form of a coating of an uncured (or not fully cured) ceramicprecursor, which has been initially dried but is later swelled by anembedding fluid. This is followed by drying of the embedding fluid,contracting a coating matrix around the additives. In some instances,the embedding fluid can include the same solvent (or another solventhaving similar characteristics) as that of the ceramic precursor priorto drying, in which case the processing conditions can be viewed aslargely parallel to those used when embedding additives into a wetcomposition. Embedding of additives is followed by the option of curingor otherwise converting the ceramic precursor to a fully condensed orrestructured glass.

In some embodiments, reactive species are selected to be initiallyoligomeric or polymeric (e.g., as opposed to monomers like TEOS or TMOS)prior to hydrolysis and condensation. Such oligomeric or polymeric formof the reactive species can promote swelling in the presence of anembedding fluid. Examples include reactive species available under thedesignations of Methyl 51, Ethyl 50, Ethyl 40, and the like. In otherembodiments, oligomeric or polymeric reactive species can be formed byreacting monomeric reactive species, such as via hydrolysis andcondensation, to reach a desired molecular weight. The oligomeric orpolymeric reactive species can be combined with monomeric reactivespecies, with the different species being miscible, partially miscible,or largely immiscible. Such oligomeric or polymeric reactive speciesalso can be used according to the left-side option of FIG. 2C, namely byincluding such oligomeric or polymeric reactive species in a coating ofa liquid ceramic precursor and embedding additives into the coatingprior to drying, optionally in the presence of an embedding fluid.

In some embodiments, reactive species can include monomers with up totwo reactive sites, such as silicones, silsesquioxanes, and the like.Upon reaction, such reactive species can form polymer chains with acontrollable amount of cross-linking, thereby promoting swelling in thepresence of an embedding fluid and facilitating embedding of additives.For example, the reactive species can include Si(OR)₂R′₂, such asSi(OCH₂CH₃)₂(CH₃)₂, which typically does not crosslink below about 400°C., can swell with an embedding fluid due to its polymeric nature, andcan be subsequently cross-linked into a glass by heating to above 400°C. Such polymeric reactive species also can be used according to theleft-side option of FIG. 2C, namely by including such polymeric reactivespecies in a coating of a liquid ceramic precursor and embeddingadditives into the coating prior to drying, optionally in the presenceof an embedding fluid.

According to some embodiments, additives can be partially embedded in aceramic or a ceramic precursor, and then covered with a relatively thinover-coating to protect the nanowires against abrasion while stillaffording surface conductivity via tunneling or breakage of theover-coating or conductivity of the over-coating. Because of theabrasion resistance afforded by the over-coating, control over an extentof embedding can be relaxed, such as by permitting under-embedding ofthe additives and enlarging a process window. In another implementation,a transparent conductor also includes an over-coating adjacent to thesurface opposite the embedding surface, which can serve to act as abuffer layer.

A manufacturing method incorporating an over-coating operation isillustrated in FIG. 4A through FIG. 4C. A coating 400 of a ceramicprecursor is formed on a substrate 402, and additives 404 are applied onand partially embedded into the coating 400, as illustrated in FIG. 4A.The substrate 402 can be composed of, for example, a polymer, anionomer, EVA, PVB, TPO, TPU, PE, PET, PETG, polycarbonate, PVC, PP,acrylic-based polymer, ABS, ceramic, glass, silicon, metal (e.g.,stainless steel or aluminum), or any combination thereof, as well as anyother material previously listed as suitable host materials. Thesubstrate 402 can serve as a temporary substrate that is subsequentlyremoved during device assembly, or can be retained in a resulting deviceas a layer or other component of the device. The ceramic precursor canbe, for example, a sol-gel precursor of a silicon dioxide glass or otherceramic, such as a solution of TEOS in ethanol, methanol, 2-propanol,n-propanol, 2-methyl-2-propanol, 1-butanol, trifluoroethanol,hexafluoropropanol, water, or any combination thereof. Furthermore, thesolvent can be pH-adjusted using HCl, HNO₃, NaOH, NH₄OH, or other acidsand bases. Non-alcohols also are suitable for embedding additives,although alcohols can be desirable to stabilize silver nanowires in someembodiments. The ceramic precursor can be applied to the substrate 402by, for example, blade coating or another suitable application method,and heated slightly to drive off excess liquid. The remaining ceramicprecursor can be referred as “A-staged” or in the “A-stage,” and can bepartially or fully cured.

Next, the additives 404 are covered with an over-coating 406, asillustrated in FIG. 4B. The over-coating 406 can be composed of the sametype of ceramic precursor as the coating 400, or can be composed of aceramic precursor that differs in some fashion. The over-coating 406 canbe applied or formed over the additives 404 by, for example, bladecoating, spraying, or another suitable application method, and thencured or otherwise processed, as illustrated in FIG. 4C. It is notedthat the over-coating 406 alternatively can be applied by lamination ordeposition techniques, such as physical vapor deposition (e.g.,sputtering, electron beam physical vapor deposition, evaporativedeposition, and pulsed laser deposition), chemical vapor deposition, andatomic layer deposition. Curing of the over-coating 406 can be carriedout by heating at a suitable temperature or within a suitabletemperature range. By way of example, heating from about 40° C. to about200° C. is one type of curing where pores can be substantiallyirreversibly shrunken, or where molecular chains can be substantiallyfully condensed. As another example, curing can be accomplished byheating at a temperature ranging from about 200° C. to about 500° C. sothat a resulting ceramic structure is rendered more rigid and ordered.Another curing method can be carried out in the presence of HCl vapor(or another acidic vapor) at room temperature or at an elevatedtemperature. A further curing method can be carried out in the presenceof ammonia vapor (or another basic vapor). Curing of the coating 400also can occur in conjunction with curing of the over-coating 406. Insome embodiments, the over-coating 406 can be conformal to the surface(as visually depicted in FIG. 4B and FIG. 4C), or the over-coating 406can be non-conformal, thereby acting as a planarization layer, which canreduce the roughness of the coating 400 and additive 404 composite.

Although a specific embodiment incorporating an over-coating operationis illustrated in FIG. 4A through FIG. 4C, other embodiments arecontemplated. For example, an over-coating operation also can beincorporated in the manufacturing methods illustrated in FIG. 2A throughFIG. 2C. As another example, an over-coating can be composed of anelectrically conductive material, a semiconducting material, or both.Examples of electrically conductive and semiconducting materials includethose listed as suitable additives herein. The use of electricallyconductive and semiconducting materials can bridge additive-additivegaps, thereby providing a desired level of electrical conductivity evenin the presence of such gaps. Additive-additive gaps, when the materialsare non-conducting, can increase junction resistance or make junctionsnon-existent, whereas, when the materials are conducting orsemiconducting, the materials can lower or minimize junction resistanceand improve junction formation. Application of an electricallyconductive or semiconducting over-coating can be carried out in avariety of ways. For example, in the case of ITO or another conductiveoxide or chalcogenide, an over-coating can be physical vapor deposited(e.g., sputtered) onto a composition with surface-exposed,surface-embedded additives. Conductive oxides and chalcogenides also canbe applied by liquid or solution deposition, as further explained in thefollowing sections. In the case of an electrically conductive polymer, acarbon-based coating, a composite material coating (e.g., a silver inkor paste), and other types of coatings, an electrically conductivematerial can be applied by coating, spraying, flow coating, and soforth.

In some implementations, the over-coating 406 can be patterned, such asan aperiodic (or non-periodic, random) pattern or a periodic pattern,such as a grid pattern, a diamond pattern, a square pattern, arectangular pattern, a triangular pattern, another polygonal pattern, awavy pattern, an angular pattern, an interconnect pattern, or anycombination thereof. In some implementations, these types of patternedover-coatings can be used for applications including solarphotovoltaics, wherein the over-coatings can be likened to the busbarsand fingers used to collect current.

To allow electrical conductivity via tunneling, a thickness of theover-coating 406 can be up to about 200 nm, such as up to about 150 nm,up to about 100 nm, up to about 90 nm, up to about 80 nm, up to about 70nm, up to about 60 nm, up to about 50 nm, up to about 40 nm, up to about30 nm, or up to about 20 nm, and down to about 5 nm, down to about 2 nm,or down to about 1 nm. In some implementations, the over-coating 406 canbe thicker, such as up to about 100 μm, up to about 10 μm, or up toabout 1 μm, depending on an electrical conductivity of the over-coatingmaterial and whether electrical or surface conductivity is desirable orundesirable. In the case of an over-coating composed of a dielectricceramic or another material, a dielectric constant of the over-coatingat room temperature can be in the range of about 1.5 to about 30, suchas from about 2 to about 25, from about 2 to about 20, from about 3 toabout 20, from about 4 to about 20, from about 5 to about 20, or fromabout 10 to about 20.

Incorporation of Additives into Transparent Conductive Matrices

Certain embodiments of transparent conductors include additives that areincorporated into host materials that are themselves electricallyconductive or semiconducting. In some embodiments, a host materialserves as a transparent conductive matrix, with incorporation ofelectrically conductive or semiconducting additives imparting improvedcharacteristics (e.g., electrical conductivity) as a result of theinteraction between the transparent conductive matrix and the additives.Some embodiments of transparent conductors include conductive oxides orchalcogenides that incorporate additives, such as microwires, nanowires,nanotubes, or both.

Transparent conductors are typically formed through the use of a dryprocess to deposit a film of a conductive oxide, such as through the useof specialized physical vapor deposition (e.g., sputtering) orspecialized chemical vapor deposition techniques. The resulting film canexhibit good transparency and good electrical conductivity. However,drawbacks to such techniques include high cost, high process complexity,intensive energy requirements, high capital expenditures for equipment,and poor productivity.

A film of a conductive oxide also can be formed through the use of a wetchemical process, such as through coating, printing, or depositing thefilm as a liquid, a solution, or a dispersion. The formulation andliquid deposition of a conductive oxide can involve applying a sol-gelprecursor of the conductive oxide or a dispersion of nanostructures ofthe conductive oxide, followed by suitable treatment to cure, coalesce,or sinter the conductive oxide into a solid film. A conductive oxidefilm formed from a sol-gel precursor can exhibit a higher smoothness ata surface, whereas a film formed from a dispersion of nanostructures canexhibit somewhat higher surface roughness. Also, the former type of filmcan be somewhat thinner than the latter type of film, while yieldingsimilar sheet resistance and transmittance. The ability to liquiddeposit conductive oxide films would allow rapid, direct, lower cost,and lower complexity application onto various substrates, includingflexible substrates. Being able to print or roll-to-roll processconductive oxide films would present a lower cost alternative tovacuum-based techniques, such as physical vapor deposition. In addition,a liquid-deposited conductive oxide film can have different filmthickness uniformity, hardness, friction, wear resistance, or adhesioncompared to physical vapor deposited films.

A current drawback of liquid-deposited conductive oxide films is that,to date, such conductive oxide films can have a higher sheet resistanceby about 2 to 3 orders of magnitude compared to conductive oxide filmsformed by a dry process. For example, sheet resistances of suchliquid-deposited conductive oxide films can be in the range of about2-10 kΩ/sq, which can be too high to meet specifications of transparentconductive electrodes for display, solar, and other applications. ITOnanoparticles, for example, can have an individual resistivity of about2×10⁻⁴ Ωcm, but films formed from such nanoparticles can have aresistivity of about 10⁻² Ωcm, indicating that much of the additionalresistance derives from grain boundaries and interfacial electronscattering as a result of the grain boundaries.

Certain embodiments of transparent conductors leverage the benefits ofliquid-deposited conductive oxide films, while addressing their drawbackof lower electrical conductivity through the incorporation of nanowiresor other electrically conductive or semiconducting additives. The use ofa conductive oxide as a host material allows additive-additive gaps tobe bridged by the conductive oxide, thereby providing a desired level ofelectrical conductivity even in the presence of such gaps and even witha density of the additives being below an electrical percolationthreshold in the absence of the conductive oxide. In other words,additive-additive conductivity can be preserved as a current passesthrough the conductive oxide between additives that are not in directcontact with one another. In the case of films formed from fused (e.g.,fully or partially fused or sintered) nanostructures of a conductiveoxide, incorporating additives into these films aids in bridgingjunctions, boosting conductivity, and maintaining desired levels oftransparency. Moreover, the conductive oxide can provide surfaceconductivity, even after embedding additives deeper into the conductiveoxide, or even with the additives distributed within the conductiveoxide through bulk incorporation. As a result, control over an extent ofembedding or a spatial distribution of additives can be relaxed, such asby permitting over-embedding or bulk incorporation of the additives andenlarging a process window. Advantageously, characteristics of theconductive oxide need not be relied as a primary or sole driver forelectrical conductivity of a resulting transparent conductor. Instead,the conductive oxide can be used to provide electrical connectionsbetween adjacent additives, thereby forming a network of additives (withgaps bridged by the conductive oxide) to provide levels of electricalconductivity at least comparable, if not superior, to conductive oxidefilms formed by a dry process. Although certain aspects of the foregoingdiscussion refer to conductive oxides, it should be understood thatthese aspects are similarly applicable to conductive chalcogenides, aswell as other electrically conductive or semiconducting materials thatcan be used as a transparent conductive matrix.

Suitable transparent conductive oxides and chalcogenides include metaloxides and metal chalcogenides that are doped or undoped. Transparentconductive oxides and chalcogenides can be crystalline, polycrystalline,or amorphous. Examples include ITO (or tin-doped indium oxide, e.g.,In₂O₃:Sn), fluorine-doped tin oxide (e.g., SnO₂:F or FTO),antimony-doped tin oxide (e.g., SnO₂:Sb), aluminum-doped zinc oxide(e.g., ZnO:Al or AZO), gallium-doped zinc oxide (e.g., ZnO:Ga),boron-doped zinc oxide (e.g., ZnO:B), indium-doped zinc oxide (e.g.,ZnO:In), cadmium oxide (doped or undoped), cadmium sulfide (doped orundoped), zinc sulfide (doped or undoped), zinc-doped aluminum oxide,and cadmium tin oxides (doped or undoped, e.g., Cd₂SnO₄). A cadmium-tinsystem (e.g., Cd—Sn alloy), lanthanum-doped strontium titanate, andyttrium-doped strontium titanate also can be used as a transparentconductive matrix. Additional examples of suitable materials includemetal salts, metal oxides, metal chalcogenides, and othermetal-containing compositions of In, Sn, Cd, Zn, Ga, Ti, Ag, Sb, Mg, Cu,Ni, Al, Fe, Co, Sc, Sr, La, Se, W, or any combination thereof.

A manufacturing method for bulk incorporation of additives into atransparent conductive matrix 504 is illustrated in FIG. 5. Referring tothe upper portion of FIG. 5, nanowires 500 (e.g., silver nanowires) aremixed with a precursor 502 of the transparent conductive matrix 504.Other types of electrically conductive or semiconducting additives canbe used in place of, or in conjunction with, the nanowires 500.

The precursor 502 can include, for example, a sol-gel precursor. Asol-gel process typically refers to a wet chemical process for materialfabrication, such as a film, a sheet, or a layer of a metal oxide. Insome embodiments, the process starts from a chemical solution (or sol)that acts as a precursor for a network (or gel) of discrete particles orpolymers. The precursor can undergo various forms of hydrolysis andpolycondensation reactions. In some embodiments, the sol graduallyevolves towards the formation of a gel-like diphasic system includingboth a liquid phase and a solid phase whose morphologies can range fromdiscrete particles to polymer networks.

A sol-gel precursor can include one or more element sources (e.g., metalsources), a solvent, and optionally a catalyst. Examples of elementsources for ITO include indium (III) chloride, indium (III)acetylacetonate, indium(III) acetate, indium (III) nitrate, indium (III)alkoxides (e.g., alkyl esters of indium(III) hydroxide analogs to TEOSand TMOS), tin(IV) chloride, tin acetate, tin isopropoxide, and tinalkoxides (e.g., alkyl esters of tin hydroxide analogs to TEOS andTMOS). Examples of element sources for aluminum-doped zinc oxide includealuminum nitrate, aluminum chloride, and zinc acetate. Example solventsinclude 2-methoxyethanol, ethanol, methanol, 2-propanol, terpineol,other alcohols, acetyl acetone, ethylene glycol, and glycerol. Examplesof catalysts include hydrochloric acid, water, and ammonia. By way ofexample, a sol-gel precursor can be a precursor of zinc oxide (doped orundoped), ITO, an oxide of aluminum and zinc, fluorine-doped tin oxide,doped cadmium oxide, or another doped or undoped metal oxide orchalcogenide. By way of example, for zinc-doped aluminum oxide, theprecursor can include a 0.1 M ethanol solution of zinc acetate plusaluminum nitrate in which a molar ratio of Zn/(Zn+Al)=0.01. By way ofexample for ITO, the precursor can include a 0.1 M ethanol solution ofindium isopropoxide plus tin acetate in which a molar ratio ofSn/(Sn+In)=0.10. More generally, a molar ratio of a doping elementrelative to a combined amount of the doping element and a main elementis in the range of about 0.01 to about 0.3, such as from about 0.02 toabout 0.25, from about 0.02 to about 0.2, or from about 0.05 to about0.15.

Additional examples of element sources for a particular metal M includeM_(x)Cl_(y), M_(x)(NO₃)_(y), M_(x)(acac)_(y), M_(x)(acetate)_(y), andM_(x)(OR), where “acac” refers to acetylacetonate, and “R” refers tohydrogen or an alkyl group. By way of example, M can be In, Sn, Al, orany other metal to create a desired transparent conductive matrix.Sol-gel precursors for metal oxides and chalcogenides are typically lessreactive than the corresponding silicon-based chemistry, so curing atsomewhat higher temperatures or the inclusion of faster leaving groups(e.g., groups other than —OR groups, or such groups with less bulky R)can be desirable.

Mixing the nanowires 500 with the precursor 502 can be carried out in anumber of ways. For example, the nanowires 500 can be mixed with asolvent, such as ethanol, and the nanowire/solvent mixture can be mixedwith the precursor 502, which can be pre-mixed with ethanol or adifferent solvent. Other examples of suitable solvents include2-propanol, ethylene glycol, methanol, toluene, methyl ethyl ketone,trifluoroethanol, tetrafluoropropanol, cyclohexanone, and the like.

Another option for mixing the nanowires 500 with the precursor 502 is tosynthesize the nanowires 500 in the presence of the precursor 502 eitherin addition to or instead of a conventional templating reagent, such aspolyvinylpyrrolidone (or PVP). Sol-gel precursors can be selected tohave similar coordination properties of a templating agent or to have asuitable functional group attached, such as a pyrrolidone group in thecase of a PVP templating reagent. The nanowires 500 can be synthesizedfrom nanoparticles through heating in the presence of a material thatpreferentially binds to a specific crystal face, thereby yieldingpreferential growth along a specific direction.

Another option for mixing the nanowires 500 with the precursor 502 isfor the nanowires 500 to be removed from a native solvent, andreconstituted or redispersed with a sol-gel solvent of the precursor502, a binder, or both. Another option for mixing the nanowires 500 withthe precursor 502 is to synthesize the nanowires 500 in-situ or justprior to mixing, for instance, via electrospinning, a liquid process,the polyol process, or another process.

In place of, or in addition to, a sol-gel precursor, the precursor 502can include nanostructures composed of a material of the transparentconductive matrix 504, such as nanoparticles of a conductive oxide,nanoparticles of a conductive chalcogenide, or both. Nanostructures of aconductive oxide or chalcogenide can be provided in the form of adispersion in a suitable liquid, and can be applied by a wet chemicalprocess similar to a sol-gel precursor. Nanostructures can besynthesized by liquid phase co-precipitation of metal sources, such asmetal salts and other metal sources similar to those listed for sol-gelprecursors. Other methods of synthesizing conductive oxide orchalcogenide nanostructures include emulsion techniques,microwave-assisted synthesis, solvothermal synthesis, laser-inducedfragmentation, and so forth. Conductive oxide or chalcogenidenanostructures can be synthesized or dispersed with polymer ligands,which can retain the nanostructures together or in close proximity withsome degree of organic cross-linking. The ligands or other stabilizationagents also can be used to impede the formation of larger agglomeratesin a deposited film, thereby leading to enhanced electrical and opticalproperties of the film. Once synthesized, nanostructures of a conductiveoxide or chalcogenide can be removed from a native solvent byprecipitation and purification, and optionally reconstituted orredispersed with a solvent, a binder, or both.

Once the nanowires 500 are mixed with the precursor 502, the resultingmixture or dispersion is applied over a substrate 506 as a coating byspraying, printing, rolling, gravure coating, slot-die coating, cupcoating, blade coating, capillary coating, immersion, dip coating, oranother suitable wet chemical process, as illustrated in the lowerportion of FIG. 5. The substrate 506 can be transparent or opaque, canbe flexible or rigid, and can be composed of, for example, a polymer, anionomer, EVA, PVB, TPO, TPU, PE, PET, PETG, polycarbonate, PVC, PP,acrylic-based polymer, ABS, ceramic, glass, silicon, metal (e.g.,stainless steel or aluminum), or any combination thereof, as well as anyother material previously listed as suitable host materials. Thesubstrate 506 can serve as a temporary substrate that is subsequentlyremoved during device assembly, or can be retained in a resulting deviceas a layer or other component of the device. Next, the mixture appliedover the substrate 506 is cured, which can include a variety of thermal,chemical, or physical treatment to form the transparent conductivematrix 504 as a solid film, sheet, or layer with the nanowires 500incorporated therein. Curing can include, for example, calcining,sintering, annealing, forming gas exposure, precursor gas exposure,ultraviolet exposure, infrared exposure, or any combination thereof. Forexample, curing can be carried out by heating to about 500° C. to about600° C., or by heating to about 50° C. in a dilute HCl environment. Inthe case of a dispersion of nanostructures of a conductive oxide orchalcogenide, curing can be carried out to at least partially coalesce,fuse, or merge the nanostructures, such as through annealing orsintering.

Referring to the lower portion of FIG. 5, a resulting transparentconductor 508 includes the nanowires 500 spatially arranged randomlythroughout a substantial portion of, or substantially the entire, volumeor thickness of the transparent conductive matrix 504. Unlikelocalization to a “planar” or “planar-like” embedded region, thenanowires 500 are arranged in a manner more closely conforming to athree-dimensional network than a two-dimensional network. Because thetransparent conductive matrix 504 can provide electrical connectionsbetween adjacent nanowires 500, physical contact between adjacentnanowires 500 is not required. For example, the transparent conductor508 can have desirable levels of electrical conductivity if thenanowires 500 are sufficiently closely spaced from one another, such aswhere a density of the nanowires 500 is such that the nanowires 500, onaverage, are no greater than about 500 nm apart, no greater than about400 nm apart, no greater than about 300 nm apart, no greater than about200 nm apart, no greater than about 100 nm apart, no greater than about50 nm apart, or no greater than about 10 nm apart. Through bulkincorporation within the transparent conductive matrix 504, thenanowires 500 are protected from decomposition when exposed to hightemperatures, thereby maintaining desired levels of electricalconductivity. Other spatial arrangements of the nanowires 500 arecontemplated. For example, the nanowires 500 can self-orient within theprecursor 502 with some degree of order prior to curing, or thenanowires 500 can bloom or migrate towards a surface of the precursor502, resulting in exposure of at least a fraction of the nanowires 500at a surface of the transparent conductive matrix 504.

A manufacturing method for surface embedding of additives into atransparent conductive matrix 604 is illustrated in FIG. 6. Referring tothe upper portion of FIG. 6, a precursor 602 of the transparentconductive matrix 604 is applied over a substrate 606 as a coating byspraying, printing, rolling, gravure coating, slot-die coating, cupcoating, blade coating, capillary coating, meniscus coating, immersion,dip coating, or another suitable wet chemical process. The precursor 602can include, for example, a sol-gel precursor of a metal oxide orchalcogenide, a dispersion of nanostructures of a metal oxide orchalcogenide, or a combination thereof. Examples of suitable materialsfor the precursor 602 are set forth above in connection with FIG. 5. Thesubstrate 606 can be transparent or opaque, can be flexible or rigid,and can be composed of, for example, a polymer, an ionomer, EVA, PVB,TPO, TPU, PE, PET, PETG, polycarbonate, PVC, PP, acrylic-based polymer,ABS, ceramic, glass, silicon, metal (e.g., stainless steel or aluminum),or any combination thereof, as well as any other material previouslylisted as suitable host materials. The substrate 606 can serve as atemporary substrate that is subsequently removed during device assembly,or can be retained in a resulting device as a layer or other componentof the device.

Next, nanowires 600 (e.g., silver nanowires) are applied to theprecursor 602, as illustrated in the middle portion of FIG. 6. Forexample, the nanowires 600 can be mixed with a solvent, such as ethanol,2-propanol, ethylene glycol, methanol, toluene, methyl ethyl ketone,trifluoroethanol, tetrafluoropropanol, cyclohexanone, and the like, andthe nanowire/solvent mixture can be applied to the precursor 602, whichcan include the same or a different solvent. Other types of electricallyconductive or semiconducting additives can be used in place of, or inconjunction with, the nanowires 600. The nanowires 600 are applied tothe precursor 602 prior to drying or curing (e.g., fully drying or fullycuring) or while it remains in a state that permits embedding of thenanowires 600 within the precursor 602. Optionally, the precursor 602can be at least partially dried or cured prior to application of thenanowires 600. It is contemplated that an embedding fluid can besimultaneously or separately applied to the precursor 602 to facilitatethe embedding of the nanowires 600. Subsequently, the precursor 602 hasat least some of the nanowires 600 partially or fully embedded into asurface of the precursor 602. Certain aspects regarding the applicationand the embedding of the nanowires 600 in FIG. 6 can be carried outusing similar processing conditions and materials as described above forFIG. 2C. In particular, and in at least certain aspects, the processingconditions for embedding the nanowires 600 into the precursor 602 ofFIG. 6 can be viewed as largely parallel to those used when embeddingthe additives 222 into the wet composition 218 of FIG. 2C.

Another option for embedding the nanowires 600 is to synthesize thenanowires 600 over the precursor 602. The nanowires 600 can be partiallyor fully embedded into a surface of the precursor 602 during orsubsequent to their synthesis.

Next, as illustrated in the lower portion of FIG. 6, the precursor 602(with the embedded nanowires 600) is cured, which can include a varietyof thermal, chemical, or physical treatment to form the transparentconductive matrix 604 as a solid film, sheet, or layer with thenanowires 600 incorporated therein. Curing can include, for example,calcining, sintering, annealing, forming gas exposure, precursor gasexposure, ultraviolet exposure, infrared exposure, or any combinationthereof. In the case of a dispersion of nanostructures of a conductiveoxide or chalcogenide, curing can be carried out to at least partiallycoalesce, fuse, or merge the nanostructures, such as through annealingor sintering.

One or more additional layers of precursors (optionally incorporatingnanowires or other additives) can be formed over the precursor 602 withthe embedded nanowires 600. The various precursor layers in a stack canbe cured together once the stack is fully formed, or each additionalprecursor layer can be cured before a subsequent precursor layer isadded to the stack.

Referring to the lower portion of FIG. 6, a resulting transparentconductor 608 includes the nanowires 600 localized within a “planar” or“planar-like” embedded region 610, which is adjacent to a top of thetransparent conductive matrix 604 and is spaced apart from the substrate606. Because the transparent conductive matrix 604 can provideelectrical connections between adjacent nanowires 600, physical contactbetween adjacent nanowires 600 is not required. For example, thetransparent conductor 608 can have desirable levels of electricalconductivity if the nanowires 600 are sufficiently closely spaced fromone another, such as where a density of the nanowires 600 is such thatthe nanowires 600, on average, are no greater than about 500 nm apart,no greater than about 400 nm apart, no greater than about 300 nm apart,no greater than about 200 nm apart, no greater than about 100 nm apart,no greater than about 50 nm apart, or no greater than about 10 nm apart.Through surface embedding within the transparent conductive matrix 604,the nanowires 600 are protected from decomposition when exposed to hightemperatures, thereby maintaining desired levels of electricalconductivity.

Another manufacturing method for incorporating additives into atransparent conductive matrix 704 is illustrated in FIG. 7.Specifically, the incorporation of additives in FIG. 7 is carried outthrough an over-coating operation. Referring to the upper portion ofFIG. 7, nanowires 700 (e.g., silver nanowires) are applied over asubstrate 706. Other types of electrically conductive or semiconductingadditives can be used in place of, or in conjunction with, the nanowires700. The nanowires 700 can be pre-formed and then applied over thesubstrate 706. Another option for applying the nanowires 700 is tosynthesize the nanowires 700 over the substrate 706. The substrate 706can be transparent or opaque, can be flexible or rigid, and can becomposed of, for example, a polymer, an ionomer, EVA, PVB, TPO, TPU, PE,PET, PETG, polycarbonate, PVC, PP, acrylic-based polymer, ABS, ceramic,glass, silicon, metal (e.g., stainless steel or aluminum), or anycombination thereof, as well as any other material previously listed assuitable host materials. The substrate 706 can serve as a temporarysubstrate that is subsequently removed during device assembly, or can beretained in a resulting device as a layer or other component of thedevice.

Optionally, the nanowires 700 can be at least partially embedded intothe substrate 706. It is contemplated that an embedding fluid can besimultaneously or separately applied to the substrate 706 to facilitatethe embedding of the nanowires 700. Certain aspects regarding theapplication and the embedding of the nanowires 700 into the substrate706 can be carried out using similar processing conditions and materialsas described above for FIG. 2A. In particular, and in at least certainaspects, the processing conditions for embedding the nanowires 700 intothe substrate 706 can be viewed as largely parallel to those used whenembedding the additives 202 into the dry composition 200 of FIG. 2A.

Next, as illustrated in the middle portion of FIG. 7, a precursor 702 ofthe transparent conductive matrix 704 is applied over the nanowires 700and the substrate 606 as an over-coating by spraying, printing, rolling,gravure coating, slot-die coating, cup coating, blade coating, capillarycoating, immersion, dip coating, or another suitable wet chemicalprocess. The precursor 702 can include, for example, a sol-gel precursorof a metal oxide or chalcogenide, a dispersion of nanostructures of ametal oxide or chalcogenide, or a combination thereof. Examples ofsuitable materials for the precursor 702 are set forth above inconnection with FIG. 5.

Next, as illustrated in the lower portion of FIG. 7, the precursor 702(over-coating the nanowires 700) is cured, which can include a varietyof thermal, chemical, or physical treatment to form the transparentconductive matrix 704 as a solid film, sheet, or layer with thenanowires 700 incorporated therein. Curing can include, for example,calcining, sintering, annealing, forming gas exposure, precursor gasexposure, ultraviolet exposure, infrared exposure, or any combinationthereof. In the case of a dispersion of nanostructures of a conductiveoxide or chalcogenide, curing can be carried out to at least partiallycoalesce, fuse, or merge the nanostructures, such as through annealingor sintering.

One or more additional layers of precursors (optionally incorporatingnanowires or other additives) can be formed over the precursor 702 withthe incorporated nanowires 700. The various precursor layers in a stackcan be cured together once the stack is fully formed, or each additionalprecursor layer can be cured before a subsequent precursor layer isadded to the stack.

Referring to the lower portion of FIG. 7, a resulting transparentconductor 708 includes the nanowires 700 localized within a “planar” or“planar-like” region 710, which is adjacent to a bottom of thetransparent conductive matrix 704 and is adjacent to the substrate 706.Because the transparent conductive matrix 704 can provide electricalconnections between adjacent nanowires 700, physical contact betweenadjacent nanowires 700 is not required. For example, the transparentconductor 708 can have desirable levels of electrical conductivity ifthe nanowires 700 are sufficiently closely spaced from one another, suchas where a density of the nanowires 700 is such that the nanowires 700,on average, are no greater than about 500 nm apart, no greater thanabout 400 nm apart, no greater than about 300 nm apart, no greater thanabout 200 nm apart, no greater than about 100 nm apart, no greater thanabout 50 nm apart, or no greater than about 10 nm apart. Becausephysical contact between adjacent nanowires 700 is not required forelectrical conductivity, the nanowires 700 can be more sparselydistributed across the substrate 706, thereby mitigating against atendency of the nanowires 700 to overlie or stack upon one another thatcan impede infiltration of the nanowires 700 by the precursor 702. Insuch fashion, the presence of gaps or voids arising from inadequateinfiltration can be reduced to yield improved performancecharacteristics. Also, through incorporation within the transparentconductive matrix 704, the nanowires 700 are protected fromdecomposition when exposed to high temperatures, thereby maintainingdesired levels of electrical conductivity.

It is noted that, in some implementations, the transparent conductivematrix 704 can be formed over the nanowires 700 without having to applythe precursor 702 over the nanowires 700. For example, a conductiveoxide can be applied by a deposition technique (e.g., physical vapordeposition) over the nanowires 700 after the nanowires 700 have beenapplied to the surface of the substrate 706. Alternatively, theprecursor 702 can be formed by a deposition technique and subsequentlyannealed to form the transparent conductive matrix 704.

Another manufacturing method for incorporating additives into atransparent conductor 808 is illustrated in FIG. 8. Specifically, theincorporation of additives in FIG. 8 can be viewed as a hybrid of themanufacturing methods illustrated in FIG. 6 and FIG. 7.

Referring to the upper portion of FIG. 8, a precursor 802 of atransparent conductive matrix 804 is applied over a substrate 806 as acoating by spraying, printing, rolling, gravure coating, slot-diecoating, cup coating, blade coating, capillary coating, immersion, dipcoating, or another suitable wet chemical process. The precursor 802 caninclude, for example, a sol-gel precursor of a metal oxide orchalcogenide, a dispersion of nanostructures of a metal oxide orchalcogenide, or a combination thereof. Examples of suitable materialsfor the precursor 802 are set forth above in connection with FIG. 5. Thesubstrate 806 can be transparent or opaque, can be flexible or rigid,and can be composed of, for example, a polymer, an ionomer, EVA, PVB,TPO, TPU, PE, PET, PETG, polycarbonate, PVC, PP, acrylic-based polymer,ABS, ceramic, glass, silicon, metal (e.g., stainless steel or aluminum),or any combination thereof, as well as any other material previouslylisted as suitable host materials. The substrate 806 can serve as atemporary substrate that is subsequently removed during device assembly,or can be retained in a resulting device as a layer or other componentof the device.

Next, nanowires 800 (e.g., silver nanowires) are applied to theprecursor 802, as illustrated in the middle portion of FIG. 8. Forexample, the nanowires 800 can be mixed with a solvent, such as ethanol,2-propanol, ethylene glycol, methanol, toluene, methyl ethyl ketone,trifluoroethanol, tetrafluoropropanol, cyclohexanone, and the like, andthe nanowire/solvent mixture can be applied to the precursor 802, whichcan include the same or a different solvent. Other types of electricallyconductive or semiconducting additives can be used in place of, or inconjunction with, the nanowires 800. The nanowires 800 are applied tothe precursor 802 prior to drying or curing (e.g., fully drying or fullycuring) or while it remains in a state that permits embedding of thenanowires 800 within the precursor 802. It is contemplated that anembedding fluid can be simultaneously or separately applied to theprecursor 802 to facilitate the embedding of the nanowires 800.Subsequently, the precursor 802 has at least some of the nanowires 800partially or fully embedded into a surface of the precursor 802. Certainaspects regarding the application and the embedding of the nanowires 800in FIG. 8 can be carried out using similar processing conditions andmaterials as described above for FIG. 2C. In particular, and in at leastcertain aspects, the processing conditions for embedding the nanowires800 into the precursor 802 of FIG. 8 can be viewed as largely parallelto those used when embedding the additives 222 into the wet composition218 of FIG. 2C.

Another option for embedding the nanowires 800 is to synthesize thenanowires 800 over the precursor 802. The nanowires 800 can be partiallyor fully embedded into a surface of the precursor 802 during orsubsequent to their synthesis.

Optionally, the precursor 802 can be at least partially dried or curedprior to application of the nanowires 800. Drying or curing of theprecursor 802 can be carried out to an extent such that the nanowires800 remain on a surface of the precursor 802, with little or noembedding into the precursor 802.

Next, as illustrated in the middle portion of FIG. 8, a precursor 810 ofa transparent conductive matrix 812 is applied over the nanowires 800and the precursor 802 as an over-coating by spraying, printing, rolling,gravure coating, slot-die coating, cup coating, blade coating, capillarycoating, immersion, dip coating, or another suitable wet chemicalprocess. The precursor 810 can include, for example, a sol-gel precursorof a metal oxide or chalcogenide, a dispersion of nanostructures of ametal oxide or chalcogenide, or a combination thereof. Examples ofsuitable materials for the precursor 810 are set forth above inconnection with FIG. 5. The precursor 810 can have the same or similarcomposition as the precursor 802, or can differ in some fashion.

Next, as illustrated in the lower portion of FIG. 8, the precursors 802and 810 are cured, which can include a variety of thermal, chemical, orphysical treatment to form the transparent conductive matrices 804 and812 as a stack of solid films, sheets, or layers with the nanowires 800incorporated therein. Curing can include, for example, calcining,sintering, annealing, forming gas exposure, precursor gas exposure,ultraviolet exposure, infrared exposure, or any combination thereof. Inthe case of a dispersion of nanostructures of a conductive oxide orchalcogenide, curing can be carried out to at least partially coalesce,fuse, or merge the nanostructures, such as through annealing orsintering.

One or more additional layers of precursors (optionally incorporatingnanowires or other additives) can be formed over the precursor 810. Thevarious precursor layers in a stack can be cured together once the stackis fully formed, or each additional precursor layer can be cured beforea subsequent precursor layer is added to the stack.

Referring to the lower portion of FIG. 8, the resulting transparentconductor 808 includes the nanowires 800 incorporated between thetransparent conductive matrices 804 and 812 and localized within a“planar” or “planar-like” region 814, which is spaced apart from thesubstrate 806 and at least partially extends above into the transparentconductive matrix 812 and below into the transparent conductive matrix804. It is also contemplated that the nanowires 800 can be substantiallyor fully localized within one of the transparent conductive matrices 804and 812. It is further contemplated that the nanowires 800 can beincorporated as a distinct layer between the transparent conductivematrices 804 and 812. Because the transparent conductive matrices 804and 812 can provide electrical connections between adjacent nanowires800, physical contact between adjacent nanowires 800 is not required.For example, the transparent conductor 808 can have desirable levels ofelectrical conductivity if the nanowires 800 are sufficiently closelyspaced from one another, such as where a density of the nanowires 800 issuch that the nanowires 800, on average, are no greater than about 500nm apart, no greater than about 400 nm apart, no greater than about 300nm apart, no greater than about 200 nm apart, no greater than about 100nm apart, no greater than about 50 nm apart, or no greater than about 10nm apart. Through incorporation within the transparent conductivematrices 804 and 812, the nanowires 800 are protected from decompositionwhen exposed to high temperatures, thereby maintaining desired levels ofelectrical conductivity.

It is noted that, in some implementations, one or more of thetransparent conductive matrices 804 and 812 can be formed without havingto apply corresponding precursors 802 and 810. For example, thetransparent conductive matrix 804 can be a conductive oxide formed byphysical vapor deposition (or another deposition technique) over thesurface of the substrate 806. The nanowires 800 then can be applied tothe surface of the transparent conductive matrix 804. Alternatively, theprecursor 802 can be formed by a deposition technique and subsequentlyannealed to form the transparent conductive matrix 804. Similarly, thetransparent conductive matrix 812 can be formed over the nanowires 800by physical vapor deposition (or another deposition technique), or theprecursor 810 can be formed by a deposition technique, and thetransparent conductive matrix 812 can be formed by annealing theprecursor 810. It is noted that, in certain implementations, one or bothof the transparent conductive matrices 804 and 812 can be formed usingphysical vapor deposition, chemical vapor deposition, atomic layerdeposition, spray coating, lamination, or other techniques.Alternatively, combinations of these techniques can be used inconjunction with formation of one of the transparent conductive matrices804 and 812 using a wet chemical process. For example, one of the twotransparent conductive matrices 804 and 812 can be formed by physicalvapor deposition, and the other can be formed using a wet chemicalprocess.

Also, instead of applying the precursor 810, an over-coating operationsimilar to that described with reference to FIG. 4A through FIG. 4C canbe performed over the nanowires 800, either before and after curing theprecursor 802. For example, an over-coating can be composed of a ceramicmaterial (e.g., a dielectric ceramic material), an electricallyconductive material, a semiconducting material, or any combinationthereof. Other aspects of such an over-coating are described above withreference to FIG. 4A through FIG. 4C, and those aspects are notrepeated.

Advantageously, the transparent conductors 508, 608, 708, and 808 ofFIG. 5 through FIG. 8, which are formed using conductive additives, canprovide levels of electrical conductivity and transparency at leastcomparable, if not superior, to conductive oxide films formed withoutsuch additives, either by a wet chemical process or by a dry process.Suitable values for electrical conductivity (in terms of sheetresistance) and transparency (in terms of transmittance) are set forthabove in the overview section for transparent conductors. For example,at a transmittance of about 85% or greater (e.g., solar flux-weightedtransmittance or one measured at another range of optical wavelengths),a sheet resistance can be no greater than about 500 Ω/sq, no greaterthan about 400 Ω/sq, no greater than about 350 Ω/sq, no greater thanabout 300 Ω/sq, no greater than about 200 Ω/sq, no greater than about100 Ω/sq, no greater than about 75 Ω/sq, no greater than about 50 Ω/sq,no greater than about 25 Ω/sq, no greater than about 15 Ω/sq, no greaterthan about 10 Ω/sq, and down to about 1 Ω/sq or about 0.1 Ω/sq, or less.Such a low sheet resistance can be attained through a synergisticinteraction between the nanowires 500, 600, 700, and 800 and thetransparent conductive matrices 504, 604, 704, 804, and 812 even thoughan intrinsic sheet resistance of the transparent conductive matrices504, 604, 704, 804, and 812 (i.e., sheet resistances of matrices 504,604, 704, 804, and 812 in the absence of the nanowires 500, 600, 700,and 800) can be at least about 800 Ω/sq, at least about 1 KΩ/sq, atleast about 1.5 KΩ/sq, or at least about 2 KΩ/sq, and up to about 10kΩ/sq or more. Stated in another way, an overall or effective sheetresistance of the transparent conductors 508, 608, 708, and 808 can beno greater than m times the intrinsic sheet resistance of thetransparent conductive matrices 504, 604, 704, 804, and 812, where m canbe about 1, about ½, about ⅕, about 1/10, about 1/20, about 1/30, about1/40, about 1/50, about 1/60, about 1/70, about 1/80, about 1/90, orabout 1/100.

Processing parameters and other considerations for embedding orotherwise incorporating additives are set forth above for someembodiments of the invention. The following lists some additionalnon-limiting considerations for engineering precursors of conductiveoxides or chalcogenides and their corresponding coating formulations ofsome embodiments:

(1) Nanowires or other additives should be compatible and stable with aprecursor to facilitate incorporation of the additives. The level ofcompatibility, for example, can be correlated with, for instance, Hansensolubility parameters and other interaction parameters between a liquiddispersion of the additives and the precursor. The level ofcompatibility also can be correlated to solvation or swelling capabilityof a liquid dispersion of the additives. In the case of incorporatingadditives into a dispersion of nanostructures of a conductive oxide orchalcogenide, relevant considerations for a liquid dispersion of theadditives can include, for example, size of the nanostructures andcapillary forces/wettability of the nano structures.

(2) A liquid-deposited formulation should have adequately small contactangles with a substrate to promote wettability. This can be addressedwith wetting agents, surface treating the substrate, or both.

(3) The liquid-deposited formulation should have adequate durabilityunder relevant industrial conditions. This can be enhanced with theaddition of one or more stabilizers.

(4) Drying and heating processes can be executed in a manner to obtainrepeatable homogenous coatings.

Devices Including Transparent Conductors

The transparent conductors described herein can be used as transparentconductive electrodes in a variety of devices. Examples of suitabledevices include solar cells (e.g., thin-film solar cells and crystallinesilicon solar cells), display devices (e.g., flat panel displays, liquidcrystal displays (“LCDs”), plasma displays, organic light emitting diode(“OLED”) displays, electronic-paper (“e-paper”), quantum dot displays,and flexible displays), solid-state lighting devices (e.g., OLEDlighting devices), touch screen devices (e.g., projected capacitivetouch screen devices, touch-on-lens projected capacitive touch screendevices, on-cell or in-cell projected capacitive touch screen devices,self capacitive touch screen devices, surface capacitive touch screendevices, and resistive touch screen devices), smart windows (or otherwindows), windshields, aerospace transparencies, electromagneticinterference shields, charge dissipation shields, and anti-staticshields, as well as other electronic, optical, optoelectronic, quantum,photovoltaic, and plasmonic devices. The transparent conductors can betuned or optimized depending on the particular application, such as workfunction matching in the context of photovoltaic devices or tuning ofthe transparent conductors to form Ohmic contacts with other devicecomponents or layers.

In some embodiments, the transparent conductors can be used aselectrodes in LCDs. FIG. 9 illustrates an example of a LCD 900 accordingto an embodiment of the invention. A backlight module 902 projects lightthrough a thin-film transistor (“TFT”) substrate 906 and a bottompolarizer 904, which is disposed adjacent to a bottom surface of the TFTsubstrate 906. A TFT 908, a pixel electrode 910, and a storage capacitor912 are disposed adjacent to a top surface of the TFT substrate 906 andbetween the TFT substrate 906 and a first alignment layer 914. A seal916 and a spacer 918 are provided between the first alignment layer 914and a second alignment layer 920, which sandwich liquid crystals 922 inbetween. A common electrode 924 and color matrices 926 are disposedadjacent to a bottom surface of a color filter substrate 928 and betweenthe color filter substrate 928 and the second alignment layer 920. Asillustrated in FIG. 9, a top polarizer 930 is disposed adjacent to a topsurface of the color filter substrate 928. Advantageously, either, orboth, of the electrodes 910 and 924 can be implemented using thetransparent conductors described herein.

In some embodiments, the transparent conductors can be used as commonelectrodes in color filter plates, which are used in LCDs. FIG. 10illustrates a color filter 1040 for use in an LCD according to anembodiment of the invention. A common electrode 1041 is disposedadjacent to an overcoat/protective layer 1042, which is depositedadjacent to Red, Green, and Blue (“RGB”) color matrices 1043, which isadjacent to a black matrix 1044, which are all disposed on a glasssubstrate 1045. The overcoat/protective layer 1042 can include, forexample, an acryl resin, a polyimide resin, a polyurethane resin, epoxy,or any combination thereof, and can be used to planarize a topography ofthe RGB color matrices 1043 and the black matrix 1044. In otherembodiments, the overcoat/protective layer 1042 can conform to thetopology of the RGB color matrices 1043 and the black matrix 1044. Inother embodiments, the overcoat/protective layer 1042 can be omitted. Insome embodiments, the black matrix 1044 can be made to be electricallyconductive, and can form electrical contact with the common electrode1041; in such embodiments, the black matrix 1044 can be viewed as abusbar for the common electrode 1041. Advantageously, the commonelectrode 1041 can be implemented using the transparent conductorsdescribed herein.

In other embodiments, the transparent conductors can be used aselectrodes in photovoltaic devices, such as solar cells. Duringoperation of a photovoltaic device, light is absorbed by a photoactivematerial to produce charge carriers in the form of electron-hole pairs.Electrons exit the photoactive material through one electrode, whileholes exit the photoactive material through another electrode. The neteffect is a flow of an electric current through the solar cell driven byincident light, which electric current can be delivered to an externalload to perform useful work.

FIG. 11 illustrates examples of thin-film solar cells 1100, 1102, and1104 according to an embodiment of the invention. In particular, thethin-film solar cell 1100 corresponds to a thin-film silicon solar cell,in which a photoactive layer 1106 formed of silicon is disposed betweena transparent conductive electrode 1108 and a back electrode 1110.Referring to FIG. 11, the thin-film solar cell 1102 corresponds to aCdTe solar cell, in which a photoactive layer 1112 formed of CdTe isdisposed between a transparent conductive electrode 1114 and a backelectrode 1118, and a barrier layer 1116 is disposed between thephotoactive layer 1112 and the transparent conductive electrode 1114.And, the thin-film solar cell 1104 corresponds to a CIGS solar cell, inwhich a photoactive layer 1120 formed of CIGS is disposed between atransparent conductive electrode 1126 and a back electrode 1124, and abarrier layer 1128 is disposed between the photoactive layer 1120 andthe transparent conductive electrode 1126. The various layers of thethin-film solar cell 1104 are disposed on top of a substrate 1122, whichcan be rigid. Advantageously, the transparent conductive electrodes1108, 1114, and 1126 can be implemented using the transparent conductorsdescribed herein. For example, in the case of the CdTe solar cell 1102,the transparent conductive electrode 1114 can serve as a superstrate fordeposition of a window layer composed of cadmium sulfide as well asother device layers. In some embodiments, an over-coating can be used totune the properties of a transparent conductive electrode, for instance,a work function. In other embodiments, mild abrasion can be used tobreak an over-coating that is present and expose underlying nanowires orother additives. It is also contemplated that the back electrodes 1110,1118, and 1124 can be similarly implemented as the transparentconductive electrodes 1108, 1114, and 1126. It is further contemplatedthat transparent conductors can be used in crystalline, polycrystalline,single crystalline, or amorphous silicon solar cells. It is furthercontemplated that by, using the transparent conductors discussed herein,fewer, thinner, more widely spaced, busbars, or a combination thereof,can be used, which can increase the performance of a solar cell by, forinstance, decreasing the amount of light blocked by the busbars. Inanother embodiment, the transparent conductors described herein, can beused to help boost the performance of a solar cell by, for instance,increasing the amount of light available to the solar cell, increasingabsorption of light into the solar cell, or a combination thereof.

In other embodiments, the transparent conductors can be used aselectrodes in touch screen devices. A touch screen device is typicallyimplemented as an interactive input device integrated with a display,which allows a user to provide inputs by contacting a touch screen. Thetouch screen is typically transparent to allow light and images totransmit through the device.

FIG. 12 illustrates an example of a projected capacitive touch screendevice 1200 according to an embodiment of the invention. The touchscreen device 1200 includes a thin-film separator 1204 that is disposedbetween a pair of patterned transparent conductive electrodes 1202 and1206, as well as a rigid touch screen 1208 that is disposed adjacent toa top surface of the transparent conductive electrode 1208. A change incapacitance occurs when a user contacts the touch screen 1208, and acontroller (not illustrated) senses the change and resolves a coordinateof the user contact. Advantageously, either, or both, of the transparentconductive electrodes 1202 and 1206 can be implemented using thetransparent conductors described herein. It is also contemplated thatthe transparent conductors can be included in resistive touch screendevices (e.g., 4-wire, 5-wire, and 8-wire resistive touch screendevices), which include a flexible touch screen and operate based onelectrical contact between a pair of transparent conductive electrodeswhen a user presses the flexible touch screen.

In other embodiments, the transparent conductors can be used aselectrodes in solid-state lighting devices. FIG. 13 illustrates anexample of an OLED lighting device 1300 according to an embodiment ofthe invention. The OLED device 1300 includes an organicelectroluminescent film 1306, which includes a Hole Transport Layer(“HTL”) 1308, an Emissive Layer (“EML”) 1310, and an Electron TransportLayer (“ETL”) 1312. Two electrodes, namely an anode 1302 and a cathode1304, are disposed on either side of the film 1306. When a voltage isapplied to the electrodes 1302 and 1304, electrons (from the cathodeD04) and holes (from the anode D02) pass into the film 1306 (stage 1).The electrons and holes recombine in the presence of light-emittingmolecules within the EML 1310 (stage 2), and light is emitted (stage 3)and exits through the cathode 1304. Advantageously, either, or both, ofthe electrodes 1302 and 1304 can be implemented using the transparentconductors described herein. It is also contemplated that thetransparent conductors can be included in OLED displays, which can beimplemented in a similar fashion as illustrated in FIG. 13.

In other embodiments, the transparent conductors can be used aselectrodes in e-paper. FIG. 14 illustrates an example of an e-paper 1400according to an embodiment of the invention. The e-paper 1400 includes atransparent conductive electrode 1402 and a bottom electrode 1404,between which are positively charged white pigments 1408 and negativelycharged black pigments 1410 dispersed in a carrier medium 1406. When a“negative” electric field is applied, the black pigments 1410 movetowards the bottom electrode 1404, while the white pigments 1408 movetowards the top transparent conductive electrode 1402, thereby renderingthat portion of the e-paper 1400 to appear white. When the electricfield is reversed, the black pigments 1410 move towards the toptransparent conductive electrode 1402, thereby rendering that portion ofthe e-paper 1400 to appear dark. Advantageously, either, or both, of theelectrodes 1402 and 1404 can be implemented using the transparentconductors described herein.

In still further embodiments, the transparent conductors can be used aselectrodes in smart windows. FIG. 15 illustrates an example of a smartwindow 1500 according to an embodiment of the invention. The smartwindow 1500 includes a pair of transparent conductive electrodes 1502and 1506, between which is an active layer 1504 that controls passage oflight through the smart window 1500. In the illustrated embodiment, theactive layer 1504 includes liquid crystals, although the active layer1504 also can be implemented using suspended particles or electrochromicmaterials. When an electric field is applied, the liquid crystalsrespond by aligning with respect to the electric field, thereby allowingthe passage of light. When the electrical field is absent, the liquidcrystals become randomly oriented, thereby inhibiting the passage oflight. In such manner, the smart window 1500 can appear transparent ortranslucent. Advantageously, either, or both, of the electrodes 1502 and1506 can be implemented using the transparent conductors describedherein. Additionally, it is contemplated that the increased smoothnessof a transparent conductor described herein (e.g., due to thelocalization of additives into a “planar” embedded region) can decreasea haze compared to other conventional structures.

EXAMPLES

The following examples describe specific aspects of some embodiments ofthe invention to illustrate and provide a description for those ofordinary skill in the art. The examples should not be construed aslimiting the invention, as the examples merely provide specificmethodology useful in understanding and practicing some embodiments ofthe invention.

Example 1 Formation and Characterization of Transparent Conductor

A spin-on glass (“SOG”) solution is formed by diluting a commerciallyavailable SOG (Flextronics SOG 20B) in a ratio of about 1 part SOG toabout 1.5 parts water. The SOG solution is coated onto a cleaned sodalime glass substrate with a blade applicator (e.g., a U-coater with0.0005″ gap) to form an SOG coating. The glass substrate can be cleanedusing a solution of a suitable detergent and de-ionized water. By way ofexample, a solution of about 2% Micro 90 detergent and about 98%de-ionized water can be used. The glass substrate can be cleaned withthis solution using a sponge, rinsed in isopropanol, and then driedusing an air knife. The SOG coating can be partially cured (“A-staged”)at about 80° C. for about 5 minutes in an oven. Next, a dispersion ofnanowires (e.g., 2.5 mg/mL, 60 nm average diameter silver nanowires,commercially available from Blue Nano North America of Corneilius, N.C.as part number SLV-NW-60) in ethanol is coated on top of the A-stagedSOG coating, such as using a blade coating technique, resulting inembedding of the silver nanowires into the SOG coating. Atetraethoxysilane (“TEOS”) precursor solution (about 0.01 M to about0.02 M) is applied over the A-staged SOG coating with embedded nanowiresusing a 0.0005″ gap U-coater. The glass-SOG-nanowire-TEOS composite isthen cured for about 60 minutes at about 70° C. in an HCl environment ofabout 1 μmole/cm³. Alternatively, curing can be done in ambientconditions or shorter time durations (e.g., a few minutes) at atemperature greater than about 40° C. Processing parameters that can beadjusted to obtain a desired coating thickness include a concentrationof the reagents, a distance between the coating applicator blade and thesubstrate, or both.

A transparent conductor was formed according to the above-describedprocedure, and yielded a surface conductivity of about 90 Ω/sq byprobing. The transparent conductor was found to be mechanically robustin that the nanowires were not removed by abrasion. Furthermore, thetransparent conductor, incorporating the nanowires, was thermally stableto at least about 550° C.

Example 2 Formation of Transparent Conductor

Indium tin oxide (“ITO”) nanoparticles are synthesized via precipitationof InCl₃ and SnCl₄.5H₂O (8 at. %), followed by drying and forming gastreatment at about 350° C., redispersal in 3,6,9-trioxadecanoic acid asa surfactant, mixed with a binder of pre-hydrolyzed3-methacryloxypropyl-trimethoxysilane for polymerization,bis[2,4,6-trimethylbenzoyl] phenyl triphosphine oxide as aphotoinitiator, and 1-propanol as the principal solvent to obtain adispersion including about 50 wt. % ITO. Silver nanowires suspended in1-propanol are then mixed into the dispersion at about 5 mg/mlconcentration. The ITO nanoparticles/silver nanowires dispersion isgravure printed or slot-die coated onto a glass substrate, and the ITOnanoparticles and silver nanowires can be sintered at about 500° C. forabout 1 hour and fused together to form a solid film. The filmincorporating the silver nanowires has a lower sheet resistance for agiven transmittance of the film.

Example 3 Formation of Transparent Conductor

About 0.40 mmol of indium acetate (99.99%), about 0.55 mL of oleylamine(70%), and about 0.60 mL of oleic acid (90%) are mixed with about 7.0 mLof hexadecane (>99% purity) in a flask at about 110° C., and thentrimethylamine N-oxide is stirred into the solution under argon. Ethanolprecipitates the solution, and, after centrifugation purification, aredispersion is carried out in isopropanol. This synthesis yieldssubstantially monodisperse, indium oxide nanoparticles of about 11 nm indiameter. A dispersion of silver nanowires in isopropanol is then mixedinto the colloid at about 1 mg/ml concentration. This dispersion is thenblade coated on a glass substrate at about 3 inches/s with a blade gapsize of about 1 mil, yielding a film of indium oxide with silvernanowires bulk incorporated therein. This film is then calcined at about600° C. to yield a solidified film that is conductive and transparent.

Example 4 Formation of Transparent Conductor

A slurry of ITO nanoparticle precursors, In(acac)₃ and Sn(acac)₂Cl₂ inoleylamine, is heated at about 250° C. for about 5 hours in argon.Ethanol is added to precipitate the nanoparticles, followed by repeatedwashing and centrifugation for purification. The ITO nanoparticles areredispersed in a suitable organic solvent for coating or embedding, suchas ethanol. Silver nanowires in ethanol are then mixed into this colloidat a concentration of about 2 mg/ml. The dispersion is then slot-diecoated onto a glass substrate. The coating with bulk incorporated silvernanowires is then thermally annealed, and processing parameters can beadjusted to tune properties of the resulting film. For example, a ratioof the metal precursors (e.g., 5:95 for Sn:In ratio) to oleylamine canbe varied to yield different sized ITO nanoparticles (e.g., 7 nmdiameter). Techniques can be used to arrange the ITO nanoparticles intovarious crystalline or amorphous configurations, such as close-packedsuperlattice structures. Seed-mediated growth of ITO nanoparticles alsocan be used to yield larger nanoparticles.

Example 5 Formation of Transparent Conductor

Al(NO₃)₃.9H₂O is added to 0.1 M zinc nitrate hexahydrate stabilized withethylene glycol in de-ionized water. The aluminum source can be variedbetween a range of about 5-9 at. % to yield various amounts of dopinglevels. Stirring can occur at about 80° C. for about 1 hour while citricacid is dropped into the solution gradually until the solution becomestransparent. Afterwards, the solution is heated at about 120° C. forsolvent evaporation, with the remainder ball milled into nanoparticlesand then oxidized in a furnace at about 700-800° C. The resulting powderis suspended in butanol, mixed with silver nanowires at a concentrationof about 3 mg/ml, and then screen printed onto a glass substrate. Thecoating is calcined in a furnace at about 600° C. to sinter thenanoparticles and nanowires together to form a solid film.

Example 6 Formation of Transparent Conductor

A transparent conductor is formed according to the following procedure:

(1) Prepare 0.1 M ethanol solution of zinc acetate and aluminum nitratesuch that a molar ratio of Zn/(Zn+Al) is about 0.009.

(2) Blade coat about 2.5 mg/mL solution of silver nanowires (Bluenano,30-60 nm diameter) onto a clean glass substrate using about 0.00075″ gapat about 3.0 in/s.

(3) Overcoat ZnO:Al sol gel using about 0.001″ gap at about 2.5 in/s.

(4) Dry in oven at about 110° C. for about 15 minutes.

(5) Overcoat ZnO:Al sol gel using about 0.00125″ gap at about 2.5 in/s.

(6) Dry in oven at about 150° C. for about 10 minutes.

(7) Heat in furnace at about 550° C. for about 30 minutes.

Example 7 Formation of Transparent Conductor

Indium tin oxide nanoparticles are synthesized via precipitation ofInCl₃ and SnCl₄.5H₂O (8 at. %), followed by drying and forming gastreatment at about 350° C., redispersal in 3,6,9-trioxadecanoic acid asa surfactant, mixed with a binder of pre-hydrolyzed3-methacryloxypropyl-trimethoxysilane for polymerization,bis[2,4,6-trimethylbenzoyl] phenyl triphosphine oxide as aphotoinitiator, and 1-propanol as the principal solvent to obtain adispersion including about 50 wt. % ITO. The dispersion of ITOnanoparticles is gravure printed or coated onto a substrate. Aftercoating the ITO nanoparticles and binder slurry out of the 1-propanolsolvent, silver nanowires or other conductive nanostructures are thencoated over the ITO nanoparticles-binder film, where the silvernanowires or other conductive nanostructures are suspended in ethanol,methanol, isopropanol, or another alcohol that permits at least partialembedding of the conductive nanostructures.

After coating the ITO nanoparticles without the inclusion of additionalconductive nanostructures, the binder cures upon UV irradiation, thesheet resistance falls from about 1,000 Ohms/sq to about 500 Ohms/sq,and subsequent forming gas annealing yields about 80% transmittance forthe ITO nanoparticle film. The ITO nanoparticles can be sintered orotherwise fused together to form a solid film, where conductivenanostructures can be embedded therein. It is expected that the fusedITO film with at least partially embedded conductive nanostructures,such as silver nanowires, will have a lower sheet resistance for a giventransmittance of the film.

Example 8 Formation of Transparent Conductor

About 0.40 mmol of indium acetate (99.99%), about 0.55 mL of oleylamine(70%), and about 0.60 mL of oleic acid (90%) are mixed with about 7.0 mLof hexadecane (>99% purity) in a flask at about 110° C., and thentrimethylamine N-oxide is stirred into the solution under argon. Ethanolprecipitates the solution, and, after centrifugation purification, aredispersion is carried out in isopropanol. This synthesis yieldssubstantially monodisperse, indium oxide nanoparticles of about 11 nm indiameter. This dispersion is then blade coated on a glass substrate atabout 3 inches/s with a blade gap size of about 1 mil, and then adispersion of silver nanowires in isopropanol of about 1 mg/mlconcentration is blade coated with the same conditions, yielding a filmof indium oxide with silver nanowires embedded therein. This film isthen calcined at about 600° C. to yield a solidified film that isconductive and transparent.

Example 9 Formation of Transparent Conductor

A slurry of ITO nanoparticle precursors, In(acac)₃ and Sn(acac)₂Cl₂ inoleylamine, is heated at about 250° C. for about 5 hours in argon.Ethanol is added to precipitate the nanoparticles, followed by repeatedwashing and centrifugation for purification. The ITO nanoparticles areredispersed in a suitable organic solvent for coating or embedding, suchas ethanol. The ITO nanoparticles are coated onto a glass substrate,followed by a time period t where an application of silver nanowiressuspended in ethanol of about 5 mg/ml concentration embeds the silvernanowires into the film of ITO nanoparticles atop the substrate.Selection of the time period t influences the degree of embedding,morphological arrangement of the silver nanowires, and the depth ofembedding of the silver nanowires, and certain conductivities andtransparencies can be attained by selection of the time period t. Theembedded film is then thermally annealed, and processing parameters canbe adjusted to tune properties of the resulting film. For example, aratio of the metal precursors (e.g., 5:95 for Sn:In ratio) to oleylaminecan be varied to yield different sized ITO nanoparticles (e.g., 7 nmdiameter). Techniques can be used to arrange the ITO nanoparticles intovarious crystalline or amorphous configurations, such as close-packedsuperlattice structures. Seed-mediated growth of ITO nanoparticles alsocan be used to yield larger nanoparticles.

Example 10 Formation of Transparent Conductor

Conventional methods to coat silver nanowires onto glass are nothigh-temperature stable. Nanowires deposited onto glass decompose atabout 550° C. (see FIG. 16, top). Nanowires coated within a conventionalbinder (hydroxypropyl methylcellulose or HPMC) similarly decompose intobeads or nanoparticles (see FIG. 16, middle). In contrast, nanowiressurface-embedded into a spin-on glass exhibit improved temperaturestability (see FIG. 16, bottom). Prior to baking, the surface-embeddedstructure has T_(luminous, excluding substrate)=85% and R_(s)=20Ohms/sq. After baking at 550° C., the surface-embedded structure hasT_(luminous, excluding substrate)=89% and R_(s)=33 Ohms/sq.

Example 11 Formation of Transparent Conductor

A glass substrate is cleaned using 2 vol % Micro90 detergent, andscrubbed with a sponge followed by de-ionized water rinse, IPA rinse,and air knife dried. The glass substrate is treated with UVO for about30 minutes prior to deposition. An ethanol solution of silver nanowiresis then blade coated on top of the glass substrate at 0.25 to 0.6 mg/mL.Subsequently, 20 nm of ITO is sputtered onto the surface. After ITOdeposition, images are taken using an optical microscope prior to baking(see FIG. 17, left) and after baking to about 600° C. for about ½ hour(see FIG. 17, right). No degradation of the nanowires is observed fromthe images after baking.

While the invention has been described with reference to the specificembodiments thereof, it should be understood by those skilled in the artthat various changes may be made and equivalents may be substitutedwithout departing from the true spirit and scope of the invention asdefined by the appended claims. In addition, many modifications may bemade to adapt a particular situation, material, composition of matter,method, or process to the objective, spirit and scope of the invention.All such modifications are intended to be within the scope of the claimsappended hereto. In particular, while the methods disclosed herein havebeen described with reference to particular operations performed in aparticular order, it will be understood that these operations may becombined, sub-divided, or re-ordered to form an equivalent methodwithout departing from the teachings of the invention. Accordingly,unless specifically indicated herein, the order and grouping of theoperations are not limitations of the invention.

What is claimed is:
 1. A transparent conductor comprising: a film of aconductive ceramic; and conductive additives at least partiallyincorporated into the film and localized within a region of the film, athickness of the region is less than an overall thickness of the film,and at least one of the conductive additives has an aspect ratio of atleast 3, wherein the transparent conductor has a sheet resistance thatis less than an intrinsic sheet resistance of the film.
 2. Thetransparent conductor of claim 1, wherein the thickness of the region isno greater than 30% of the overall thickness of the film.
 3. Thetransparent conductor of claim 1, wherein the sheet resistance of thetransparent conductor is no greater than 200 Ω/sq.
 4. The transparentconductor of claim 1, wherein the sheet resistance of the transparentconductor is no greater than ⅕ of the intrinsic sheet resistance of thefilm.
 5. The transparent conductor of claim 1, wherein the conductiveceramic is a doped metal oxide.
 6. The transparent conductor of claim 1,wherein the conductive additives include metallic nanowires.
 7. Thetransparent conductor of claim 1, wherein at least one of the conductiveadditives is fully localized within the film.
 8. A manufacturing methodof a transparent conductor, comprising: mixing conductive additives witha precursor of a conductive ceramic to form a mixture; applying themixture as a coating over a substrate; and curing the coating to form afilm of the conductive ceramic, wherein the conductive additives are atleast partially incorporated into the film.
 9. The manufacturing methodof claim 8, wherein the mixture includes a liquid phase, and applyingthe mixture includes applying the mixture as a wet coating over thesubstrate.
 10. The manufacturing method of claim 8, wherein theprecursor is a sol-gel precursor of the conductive ceramic.
 11. Themanufacturing method of claim 10, wherein the sol-gel precursor is asolution of a source of a main element and a source of a doping element.12. The manufacturing method of claim 8, wherein the precursor includesnanostructures of the conductive ceramic.
 13. The manufacturing methodof claim 12, wherein the precursor is a dispersion of the nanostructuresin a liquid.
 14. The manufacturing method of claim 8, wherein theconductive ceramic is a conductive oxide.
 15. The manufacturing methodof claim 8, wherein the conductive additives include metallic nanowires.16. A manufacturing method of a transparent conductor, comprising:providing a precursor of a conductive ceramic; applying the precursor asa coating over a substrate; applying conductive additives to the coatingto embed the conductive additives into the coating; and curing thecoating to form a film of the conductive ceramic, wherein the conductiveadditives are at least partially embedded into the film.
 17. Themanufacturing method of claim 16, wherein the precursor includes aliquid phase, and applying the precursor includes applying the precursoras a wet coating over the substrate.
 18. The manufacturing method ofclaim 16, wherein the precursor is a sol-gel precursor of the conductiveceramic.
 19. The manufacturing method of claim 16, wherein the precursorincludes nanostructures of the conductive ceramic.
 20. The manufacturingmethod of claim 16, wherein applying the conductive additives to thecoating includes applying an embedding fluid to facilitate embedding ofthe conductive additives into the coating.
 21. The manufacturing methodof claim 16, wherein the conductive additives are localized within a topregion of the film, and a thickness of the top region is less than anoverall thickness of the film.
 22. The manufacturing method of claim 16,wherein the conductive additives include metallic nanowires.
 23. Amanufacturing method of a transparent conductor, comprising: applyingconductive additives over a substrate; providing a precursor of aconductive ceramic; applying the precursor as a coating over theconductive additives and the substrate; and curing the coating to form afilm of the conductive ceramic, wherein the conductive additives are atleast partially incorporated into the film.
 24. The manufacturing methodof claim 23, wherein the precursor includes a liquid phase, and applyingthe precursor includes applying the precursor as a wet coating over theconductive additives and the substrate.
 25. The manufacturing method ofclaim 23, wherein the precursor is a sol-gel precursor of the conductiveceramic.
 26. The manufacturing method of claim 23, wherein the precursorincludes nanostructures of the conductive ceramic.
 27. The manufacturingmethod of claim 23, wherein applying the conductive additives over thesubstrate includes at least partially embedding the conductive additivesinto the substrate.
 28. The manufacturing method of claim 27, whereinapplying the conductive additives over the substrate includes applyingan embedding fluid to facilitate embedding of the conductive additivesinto substrate.
 29. The manufacturing method of claim 23, wherein theconductive additives are localized within a bottom region of the film,and a thickness of the bottom region is less than an overall thicknessof the film.
 30. The manufacturing method of claim 23, wherein theconductive additives include metallic nanowires.